Silicon-containing resists underlayer film-forming composition having phenyl group-containing chromophore

ABSTRACT

The present invention provides a resist underlayer film-forming composition for lithography for forming a resist underlayer film that can be used as a hard mask with use of hydrolysis-condensation product of a hydrolyzable silane which also absorbs KrF laser. A resist underlayer film-forming composition for lithography comprising, as a silane, a hydrolyzable silane, a hydrolysis product thereof, or a hydrolysis-condensation product thereof, wherein the hydrolyzable silane includes a hydrolyzable silane of Formula (1):
 
R 1   a R 2   b Si(R 3 ) 4−(a+b)   Formula (1)
 
[where R 1  is an organic group of Formula (2):
 
                         
and is bonded to a silicon atom through a Si−C bond; R 3  is an alkoxy group, an acyloxy group, or a halogen group; a is an integer of 1; b is an integer of 0 to 2; and a+b is an integer of 1 to 3], and a ratio of sulfur atoms to silicon atoms is 7% by mole or more in the whole of the silane. A resist underlayer film obtained by applying the resist underlayer film-forming composition onto a semiconductor substrate and baking it.

TECHNICAL FIELD

The present invention relates to a composition for forming an underlayerfilm between a substrate and a resist (such as photoresist or electronresist) for use in the manufacture of semiconductor devices.Specifically, the present invention relates to a resist underlayerfilm-forming composition for lithography for forming an underlayer filmused as a layer under a photoresist in a lithography process for themanufacture of semiconductor devices. Furthermore, the present inventionrelates to a method for forming a resist pattern using the underlayerfilm-forming composition.

BACKGROUND ART

In the manufacture of semiconductor devices, fine processing bylithography using photoresists been conventionally performed. The fineprocessing is a processing method including: forming a photoresist thinfilm on a semiconductor substrate such as a silicon wafer; irradiatingthe thin film with an active ray such as ultraviolet ray through a maskpattern having a semiconductor device pattern depicted therein; carryingout development; and etching the substrate with the obtained photoresistpattern as a protective film, thereby forming fine projections anddepressions corresponding to the pattern on the surface of thesubstrate. However, with the higher integration of semiconductor devicesin recent years, an active ray to be used tends to have a shorterwavelength, namely, shift front KrF excimer laser (248 nm) to ArFexcimer laser (193 nm). Accordingly, the influence of reflection of theactive ray on a semiconductor substrate has become a serious problem.

A film known as a hard mask containing metal elements, such as siliconand titanium, has been used as an underlayer film between asemiconductor substrate and a photoresist. In this case, the photoresistand the hard mask are significantly different in components, and therates to remove these by dry etching are greatly dependent on the typesof gas used for dry etching. Therefore, the appropriate selection of agas type allows the hard mask to be removed by dry etching without alarge reduction in the film thickness of the photoresist. Thus, in themanufacture of semiconductor devices in recent years, a resistunderlayer film has been increasingly disposed between a semiconductorsubstrate and a photoresist to achieve various effects such as ananti-reflection effect. Compositions for resist underlayer films havebeen studied, but, because of the diversity of characteristics demandedof the compositions, development of novel materials for resistunderlayer films has been desired.

For example, a resist underlayer film including a polysiloxanecontaining a silane having a sulfone structure has been proposed (referto Patent Document 1).

A resist underlayer film including a polysiloxane containing a silanehaving a sulfonamide structure has been proposed (refer to PatentDocument 2).

A resist underlayer film including a polysiloxane containing a silanehaving a sulfone structure and an amine structure has been proposed(refer to Patent Document 3).

Resist underlayer films including a polysiloxane containing a silanehaving a sulfide bond have been proposed (refer to Patent Documents 4and 5).

PRIOR ART DOCUMENTS Patent Documents

-   -   Patent Document 1: WO 2013/022099    -   Patent Document 2: WO 2011/033965    -   Patent Document 3: WO 2013/191203    -   Patent Document 4: WO 2010/140551    -   Patent Document 5: Japanese Unexamined Patent Application

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

It is an object of the present invention to provide a resist underlayerfilm-forming composition for lithography that can be used formanufacturing semiconductor devices. Specifically, it is an object ofthe present invention to provide a resist underlayer film-formingcomposition for lithography for forming a resist underlayer film thatcan be used as a hard mask. Furthermore, it is an object of the presentinvention to provide a resist underlayer film-forming composition forlithography for forming a resist underlayer film that can be used as ananti-reflective coating. Furthermore, it is an object of the presentinvention to provide a resist underlayer film for lithography which doesnot intermix with a resist and whose dry etching rate is higher thanthat of the resist, and to provide a resist underlayer film-formingcomposition for forming the underlayer film.

In particular, it is an object of the present invention to provide aresist underlayer film-forming composition for forming a resistunderlayer film that allows an excellent resist pattern shape to beformed when a resist as an upper layer is exposed to light and developedusing an alkaline developing solution or an organic solvent, and thatallows a rectangular resist pattern to be transferred to an underlayerby subsequent dry etching.

Furthermore, there has been a problem in that, in the case where aresist underlayer film formed from a resist underlayer film-formingcomposition is used as a hard mask, when a condensed ring structure of,for example, anthracene or phenanthrene, or a naphthalimide structure isused as a chromophore for KrF laser in a lithography process using theexposure wavelength of KrF (248 nm), the distillation purification ofthese components is difficult because the molecular weight thereof islarge, and, as a result, the removal of metals as impurities in themanufacture of semiconductors is difficult. It is an object of thepresent invention to provide a resist underlayer film-formingcomposition that absorbs KrF laser and includes a chromophore having alow molecular weight, thereby allowing easy distillation purification.

Means for Solving the Problem

The present invention provides:

according to a first aspect, a resist underlayer film-formingcomposition for lithography; the composition comprising, as a silane, ahydrolyzable silane, a hydrolysis product thereof, or ahydrolysis-condensation product thereof, in which the hydrolyzable slimeincludes a hydrolyzable silane of Formula (1):R¹ _(a)R² _(b)Si(R³)_(4−(a+b))  Formula (1)[where R¹ is an organic group of Formula (2):

(where each of X and Y is an oxygen atom or a sulfur atom, provided thatX and Y are not the same atom at the same time; R⁶ is an optionallysubstituted C₁₋₁₀ alkyl group; R⁴ is an optionally substituted C₁₋₁₀alkylene group; R⁵ is an optionally substituted C₁₋₁₀ alkyl group; and nis an integer of 0 to 4), and is bonded to a silicon atom through a Si—Cbond; R² is an alkyl group, an aryl group; a halogenated alkyl group, ahalogenated aryl group, an alkoxyaryl group, an alkenyl group, or anorganic group having an epoxy group, acryloyl group, a methacryloylgroup, a mercapto group, an amino group, or a cyano group, and is bondedto a silicon atom through a Si—C bond; R³ is an alkoxy group, an acyloxygroup, or a halogen group; a is an integer of 1; b is an integer of 0 to2; and a+b is an integer of 1 to 3], and a ratio of sulfur atoms tosilicon atoms is 7% by mole or more in the whole of the silane;

according to a second aspect, the resist underlayer film-formingcomposition for lithography according to the first aspect, in which theratio of sulfur atoms to silicon atoms is 7% by mole to 50% by mole inthe whole of the silane;

according; to a third aspect, the resist underlayer film-formingcomposition according to the first aspect or the second aspect, in whichthe hydrolyzable silane is a combination of the hydrolyzable silane ofFormula (1) and another hydrolyzable silane, and the other hydrolyzablesilane is at least one hydrolyzable silane selected from the groupconsisting of a hydrolyzable silane of Formula (3):R⁷ _(c)Si(R⁸)_(4−c)  Formula (3)(where R⁷ is an alkyl, group, an aryl group, a halogenated alkyl group,a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or anorganic group having an epoxy group, acryloyl group, a methacryloylgroup, a mercapto group, or a cyano group, and is bonded to a siliconatom through a Si—C bond; R⁸ is an alkoxy group, an acyloxy group, or ahalogen group; and c is an integer of 0 to 3) and a hydrolyzable silaneof Formula (4):

R⁹ _(d)Si(R¹⁰)_(3−d)

₂Y^(R) _(e)  Formula (4)(where R⁹ is an alkyl group and is bonded to a silicon atom through aSi—C bond; R¹⁰ is an alkoxy group, an acyloxy group, or a halogen group;Y^(R) is an alkylene group or an arylene group; d is an integer of 0 or1; and e is an integer of 0 or 1);

according to a fourth aspect, a resist underlayer film-formingcomposition, the composition comprising, as an underlayer film-formingpolymer, a hydrolysis-condensation product of a hydrolyzable silanecomprising a combination of the hydrolyzable silane of Formula (1)according to the first aspect and the hydrolyzable silane of Formula (3)according to the third aspect;

according to a fifth aspect, the resist underlayer film-formingcomposition according to any one of the first aspect to the fourthaspect, further comprising an acid as a hydrolysis catalyst;

according to a sixth aspect, the resist underlayer film-formingcomposition according to any one of the first aspect to the fifthaspect, further comprising water;

according to a seventh aspect, a resist underlayer film obtained byapplying the resist underlayer film-forming composition according to anyone of the first aspect to the sixth aspect onto a semiconductorsubstrate and baking the applied resist underlayer film-formingcomposition;

according to an eighth aspect, a method for manufacturing asemiconductor device, the method comprising the steps of: applying theresist underlayer film-forming composition according to an one of thefirst aspect to the sixth aspect onto a semiconductor substrate, andbaking the applied resist underlayer film-forming composition to form aresist underlayer film; applying a resist composition onto theunderlayer film to form a resist film; exposing the resist film tolight; developing the resist after the exposure to obtain a resistpattern; etching the resist underlayer film with the resist pattern; andprocessing the semiconductor substrate with the patterned resistunderlayer film;

according to a ninth aspect, a method for manufacturing a semiconductordevice, the method comprising the steps of: forming an organicunderlayer film on a semiconductor substrate; applying the resistunderlayer film-forming composition according to any one of the firstaspect to the sixth aspect onto the organic underlayer film, and bakingthe applied resist underlayer film-forming composition to form a resistunderlayer film; applying a resist composition onto the resistunderlayer film to form a resist film; exposing the resist film tolight; developing the resist after the exposure to obtain a resistpattern; etching the resist underlayer film with the resist pattern;etching the organic underlayer film with the patterned resist underlayerfilm; and processing the semiconductor substrate with the patternedorganic underlayer film; and

according to a tenth aspect, a silane of Formula (1′):R¹ _(a)R² _(b)Si(R³)_(4−(a+b))  Formula (1′)[where R¹ is an organic group of Formula (2′):

(where each of X and Y is an oxygen atom or a sulfur atom, provided thatX and Y are not the same atom at the same time; R⁶ is an optionallysubstituted C₁₋₁₀ alkyl group; R⁴ is an optionally substituted C₁₋₁₀alkylene group; R⁵ is an optionally substituted C₁₋₁₀ alkyl group; and nis an integer of 0 to 4) and bonded to a silicon atom through a Si—Cbond; R² is an alkyl group, an aryl group, a halogenated alkyl group, ahalogenated aryl group, an alkoxyaryl group, an alkenyl group, or anorganic group having an epoxy group, an acryloyl group, a methacryloylgroup, a mercapto group, an amino group, or a cyano group, and is bondedto a silicon atom through a Si—C bond; R³ is an alkoxy group, an acyloxygroup, or a halogen group; a is an integer of 1; b is an integer of 0 to2; and a+b is an integer of 1 to 3].

Effects of the Invention

The resist underlayer film-forming composition for lithography of thepresent invention is capable of being used for the manufacture ofsemiconductor devices.

Furthermore, the resist underlayer film-forming composition forlithography of the present invention is capable of being used as a hardmask, and furthermore, is capable of being used as an anti-reflectivecoating, depending on the wavelength of an exposure light to be used.Furthermore, the composition does not intermix with a resist, and thedry etching rate of the composition is higher than that of the resist.Therefore, the resist underlayer film-forming composition forlithography of the present invention allows an excellent resist patternshape to be formed when a resist serving as an upper layer is exposed tolight and developed using an alkaline developing solution or an organicsolvent, and allows a rectangular resist pattern to be transferred to anunderlayer by subsequent dry etching.

Furthermore, a hydrolyzable silane included in the resist underlayerfilm-forming composition of the present invention has a low molecularweight, and therefore can be easily purified by distillation.Accordingly, the resist underlayer film-forming composition of thepresent invention is formed into a resist underlayer film having a lowmetal impurity content, and therefore, makes it possible to manufacturea semiconductor product having less impurities even in a lithographyprocess using the exposure wavelength of KrF (248 nm).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing an NMR spectrum of Compound 1.

FIG. 2 is a graph showing an NMR spectrum of Compound 2.

FIG. 3 is a graph showing an NMR spectrum of Compound 3.

FIG. 4 is a graph showing an NMR spectrum of Compound 4.

FIG. 5 is a graph showing an NMR spectrum of Compound 5.

FIG. 6 is a graph showing an NMR spectrum of Compound 6.

FIG. 7 is a graph showing an NMR spectrum of Comparative Compound 1.

MODES FOR CARRYING OUT THE INVENTION

The present invention provides a resist underlayer film-formingcomposition for lithography, the composition comprising, as a silane, ahydrolyzable silane, a hydrolysis product thereof, or ahydrolysis-condensation product thereof, in which the hydrolyzablesilane includes a hydrolyzable silane of Formula (1), and the ratio ofsulfur atoms to silicon atoms in the whole of the silane is 7% by moleor more.

In Formula (1), R¹ is an organic group of Formula (2) and is bonded to asilicon atom through a Si—C bond. R² is an alkyl group, an aryl group, ahalogenated alkyl group, a halogenated aryl group, an alkoxyaryl group,an alkenyl group, or an organic group having an epoxy group, an acrylgroup, a methacryloyl group, a mercapto group, an amino group, or acyano group, and is bonded to a silicon atom through a Si—C bond. R³ isan alkoxy group, an acyloxy group, or a halogen group. a is an integerof 1, b is an integer of 0 to 2, and a+b is an integer of 1 to 3.

In Formula (2), each of X and Y is an oxygen atom or a sulfur atom.However, X and Y are not the same atom at the same time. That is, in thepresent invention, X is an oxygen atom and Y is a sulfur atom, or,alternatively, X is a sulfur atom and Y is an oxygen atom. The use of asulfur atom enables a sulfide bond to be formed. The use of an oxygenatom enables an ether bond to be formed.

R⁶ is an optionally substituted C₁₋₁₀ alkyl group, R⁴ is an optionallysubstituted C₁₋₁₀ alkylene group, and R⁵ is an optionally substitutedC₁₋₁₀ alkyl group. n is an integer of 0 to 4. A portion of R⁴ is bondedto the Si atom.

In the whole of the silane, the silane of Formula (1) may be used in arange of 50% by mole or less, 5% by mole to 50% by mole, 7% by mole to50% by mole, 7% by mole to 40% by mole, 7% by mole to 35% by mole, 7% bymole to 30% by mole, 7% by mole to 20% by mole, 10% by mole to 50% bymole, 10% by mole to 45% by mole, 10% by mole to 40% by mole, 10% bymole to 35% by mole, 10% by mole to 30% by mole, or 7% by mole to 20% bymole.

The resist underlayer film-forming composition of the present inventionincludes a hydrolyzable silane of Formula (1), or a hydrolyzable silaneof Formula (1) and another hydrolyzable silane (for example, ahydrolyzable silane of Formula (3)), a hydrolysis product thereof, or ahydrolysis-condensation product thereof, and a solvent. Furthermore, theresist underlayer film-forming composition may include an acid, water,alcohol, a curing catalyst, an acid generator, other organic polymers, alight-absorbing compound, and a surfactant, as optional components.

The resist underlayer film forming composition of the present inventionhas a solid content of, for example, 0.1% by mass to 50% by mass, 0.1%by mass to 30% by mass, or 0.1% by mass to 25% by mass. Here, the solidcontent means a content obtained by subtracting a solvent component fromall components of the resist underlayer film-forming composition.

The ratio of the hydrolyzable silane, the hydrolysis product thereof,and the hydrolysis-condensation product thereof in the solid content is20% by mass or more, for example, 50% by mass to 100% by mass; 60% bymass to 99% by mass, or 70% by mass to 99% by mass.

The above-mentioned alkyl group may be a linear or branched C₁₋₁₀ alkylgroup, and examples of the alkyl group include methyl group, ethylgroup, n-propyl group, i-propyl group, n-butyl group, i-butyl group,s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group,2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propylgroup, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group,1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group,2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentylgroup, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group,1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group,2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butylgroup, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group,1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and1-ethyl-2-methyl-n-propyl group.

Furthermore, a cyclic alkyl group may be used, and examples of thecyclic C₁₋₁₀ alkyl group include cyclopropyl group, cyclobutyl group,1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentylgroup, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group,3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group,2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group,2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group,2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group,1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutylgroup, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group,2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group,2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group,1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group,1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group,1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group,2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group,2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group,and 2-ethyl-3-methyl-cyclopropyl group. These examples are also appliedto an alkyl group portion of the above-mentioned halogenated alkylgroup.

The above-mentioned alkylene group may be, for example, an alkylenegroup derived from the above-mentioned alkyl group. Examples of thealkylene group include methylene group derived from methyl group,ethylene group derived from ethyl group, and propylene group derivedfrom propyl group.

The above-mentioned alkenyl group may be, for example, a C₂₋₁₀ alkenylgroup, and examples of the alkenyl group include ethenyl group,1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenylgroup, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group,2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenylgroup, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group,3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group,1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenylgroup, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group,2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenylgroup, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group,1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group,1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group,1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group,1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group,5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group,1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenylgroup, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group,2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group,2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group,3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group,3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenylgroup, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group,4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group,1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group,1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group,1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group,1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group,1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group,2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group,2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group,2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group,1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenylgroup, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group,2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenylgroup, 1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group,1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group,1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group,1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group,1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group,2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group,2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group,2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group,3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group,3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group,3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenylgroup, and 3-cyclohexenyl group.

The above-mentioned aryl group may be, for example, a C₆₋₂₀ aryl group,and examples of the aryl group include phenyl group, o-methylphenylgroup, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group,m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group,p-mercaptophenyl group, o-methoxyphenyl group, p-methoxyphenyl group,p-aminophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthylgroup, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group,1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group,2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, and9-phenanthryl group. These examples are also applied to aryl groupportions of the above-mentioned halogenated aryl group and theabove-mentioned alkoxyaryl group.

Furthermore, examples of the above-mentioned arylene group may includedivalent organic groups derived from the above-mentioned aryl groups.

Examples of the above-mentioned organic group having an epoxy groupinclude glycidoxymethyl, glycidoxyethyl, glycidoxypropyl,glycidoxybutyl, and epoxycyclohexyl.

Examples of the above-mentioned organic group having an acryloyl groupinclude acryloylmethyl, acryloylethyl, and acryloylpropyl.

Examples of the above-mentioned organic group having a methacryloylgroup include methacryloylmethyl, methacryloylethyl, andmethacryloylpropyl.

Examples of the above-mentioned organic group having a mercapto groupinclude ethylmercapto group, butylmercapto group, hexylmercapto group,and octylmercapto group.

Examples of the above-mentioned organic group having an amino groupinclude aminomethyl group, aminoethyl group, and aminopropyl group.

Examples of the above-mentioned organic group having a cyano groupinclude cyanoethyl group and cyanopropyl group.

The above-mentioned alkoxy group may be, for example, an alkoxy grouphaving a C₁₋₂₀ linear, branched, or cyclic alkyl portion. Examples ofthe alkoxy group include methoxy group, ethoxy group, n-propoxy group,i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group,t-butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group,2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxygroup, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group,1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group,2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group,4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group,1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group,2,2-dimethyl-n-butoxy group, 2,3-di ethyl-n-butoxy group,3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxygroup, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group,1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group;and examples of the cyclic alkoxy group include cyclopropoxy group,cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxygroup, cyclopentyloxy group, 1-methyl-cyclobutoxy group,2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group,1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group,1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxygroup, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group,3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group,2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group,1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group,2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group,2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group,1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group,1-i-propyl-cyclopropoxy group, 2-i-propyl-cyclopropoxy group,1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group,2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group,2-ethyl-1-methyl-cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxygroup, and 2-ethyl-3-methyl-cyclopropoxy group. These examples are alsoapplied to an alkoxy group portion of the above-mentioned alkoxyarylgroup.

The above-mentioned acyloxy group may be, for example, a C₂₋₂₀ acyloxygroup, and examples of the acyloxy group include methylcarbonyloxygroup, ethylcarbonyloxy group, n-propylcarbonyloxy group,i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butylcarbonyloxygroup, s-butylcarbonyloxy group, t-butylcarbonyloxy group,n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group,2-methyl-n-butylcarbonyloxy group, 3-methyl-n-butylcarbonyloxy group,1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxygroup, 2,2-dimethyl-n-propylcarbonyloxy group,1-ethyl-n-propylcarbonyloxy group, n-hexylcarbonyloxy group,1-methyl-n-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group,3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group,1,1-dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxygroup, 1,3-dimethyl-n-butylcarbonyloxy group,2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxygroup, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxygroup, 2-ethyl-n-butylcarbonyloxy group,1,1,2-trimethyl-n-propylcarbonyloxy group,1,2,2-trimethyl-n-propylcarbonyloxy group,1-ethyl-1-methyl-n-propylcarbonyloxy group,1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, andtosylcarbonyloxy group.

Examples of the above-mentioned halogen group include a fluorine atom, achlorine atom, a bromine atom, and an iodine atom. These examples arealso applied to halogen group portions of the above-mentionedhalogenated alkyl group and the above-mentioned halogenated aryl group.

Examples of the hydrolyzable silane of Formula (1) are as follows.

In the present invention, the hydrolyzable silane is a combination ofthe hydrolyzable silane of Formula (1) and another hydrolyzable silane,and as the other hydrolyzable silane, at least one hydrolyzable silaneselected from the group consisting of hydrolyzable silanes of Formula(3) and Formula (4) below may be used.R⁷ _(c)Si(R⁸)_(4−c)  Formula (3)

In Formula (3), R⁷ is an alkyl group, an aryl group, a halogenated alkylgroup, a halogenated aryl group, an alkoxyaryl group, an alkenyl group,or an organic group having an epoxy group, an acryloyl group, amethacryloyl group, a mercapto group, or a cyano group, and is bonded toa silicon atom through a Si—C bond; R⁸ is an alkoxy group, an acyloxygroup, or a halogen group; and c is an integer of 0 to 3.

R⁹ _(d)Si(R¹⁰)_(3−d)

₂Y^(R) _(e)  Formula (4)

In Formula (4), R⁹ is an alkyl group and is bonded to a silicon atomthrough a Si—C bond; R¹⁰ is an alkoxy group, an acyloxy group, or ahalogen group; Y^(R) is an alkylene group or an arylene group; d is aninteger of 0 or 1; and e is an integer of 0 or 1.

As the alkyl group; the aryl group; the halogenated alkyl group; thehalogenated aryl group; the alkoxyaryl group; the alkenyl group; or theorganic group having an epoxy group, an acryloyl group, a methacryloylgroup, a mercapto group, or a cyano group; the alkoxy group; the acyloxygroup; the halogen group; the alkylene group; and the arylene group,which are defined in Formula (3) and Formula (4), the above-mentionedexamples may be used.

Examples of the silicon-containing compound of Formula (3) includetetramethoxysilane, tetrachlorosilane, tetraacetoxysilane,tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane,tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane,methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane,methyltriamyloxysilane, methyltriphenoxysilane,methyltribenzyloxysilane, methyltriphenethyloxysilane,glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane,α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane,β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane,α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane,β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane,γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane,γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane,α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane,γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane,δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane,(3,4-epoxycyclohexyl)methyltrimethoxysilane,(3,4-epoxycyclohexyl)methyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethyltripropoxysilane,β-(3,4-epoxycyclohexyl)ethyltributoxysilane,β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane,γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)propyltriethoxysilane,δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane,δ-(3,4-epoxycyclohexyl)butyltriethoxysilane,glycidoxymethylmethyldimethoxysilane,glycidoxymethylmethyldiethoxysilane,α-glycidoxyethylmethyldimethoxysilane,α-glycidoxyethylmethyldiethoxysilane,β-glycidoxyethylmethyldimethoxysilane,β-glycidoxyethylethyldimethoxysilane,α-glycidoxypropylmethyldimethoxysilane,α-glycidoxypropylmethyldiethoxysilane,β-glycidoxypropylmethyldimethoxysilane,β-glycidoxypropylethyldimethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropylmethyldipropoxysilane,γ-glycidoxypropylmethyldibutoxysilane,γ-glycidoxpropylmethyldiphenoxysilane,γ-glycidoxypropylethyldimethoxysilane,γ-glycidoxypropylethyldiethoxysilane,γ-glycidoxypropylvinyldimethoxysilane,γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane,vinyltriacctoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane,methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane,methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane,methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane,methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane,methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane,methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane,ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane,ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane,ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane,ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane,isopropoxyphenyltrimethoxysilane, isopropoxyphertyltriethoxysilane,isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane,isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane,isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane,t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane,t-butoxyphenyltriacetoxysilane, t-hutoxyphenyltrichlorosilane,t-butoxybenzyltrimethoxysilane, t-butoxyhenzyltriethoxysilane,t-butoxybenzyltriacetoxysilane, t-butoxybenzyltrichlorosilane,methoxynaphthyitrimethoxysilane, methoxynaphthyltriethoxysilane,methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane,ethoxynaphthyltrimethoxysilane, ethoxynaphathyltriethoxysilane,ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane,γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane,γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane,γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane.γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane,chloromethyltrimethoxysilane, chloromethyltriethoxysilane,dimethyldimethoxysilane, phenylmethyldimethoxysilane,dimethyldiethoxysilane, phenylmethyldiethoxysilane,γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane,dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane,methylvinyldimethoxysilane, and methylvinyldiethoxysilane.

Furthermore, the following hydrolyzable silanes may be used.

Examples of the silicon-containing compound of Formula (4) includemethylenebistrimethoxysilane, methylenebistrichlorosilane,methylenebistriacetoxysilane, ethylenebistriethoxysilane,ethylenebistrichlorosilane, ethylenebistriacetoxysilane,propylenebistriethoxysilane, butylenebistrimethoxysilane,nhenylenebistrimethoxysilane, phenylenebistriethoxysilane,phenylenebismethyldiethoxysilane, phenvienebismethyldimethoxysilane,naphthylenebistrimethoxysilane, bistrimethoxydisilane,bistriethoxydisilane, bisethyldiethoxydisilane, andbismethyldimethoxydisilane.

In the present invention, furthermore, a silane having a sulfone groupand a silane having a sulfonamide group may be used as the hydrolyzablesilane, and examples of these silanes are as follows.

Specific examples of the hydrolysis-condensation product (polysiloxane)used in the present invention are as follows.

The above-mentioned hydrolysis-condensation products(polyorganosiloxane) of the hydrolyzable silanes each have aweight-average molecular weight of 1,000 to 1,000,000, or 1,000 to100,000. The molecular weights of these hydrolysis-condensation productsare obtained by GPC analysis in terms of polystyrene.

The GPC measurement can be performed under conditions, for example,using a GPC apparatus (the trade name HLC-8220GPC, manufactured by TosohCorporation), GPC columns (the trade name Shodex KF803L, KF802, andKF801, manufactured by Showa Denko K.K.), a column temperature of 40°C., tetrahydrofuran as an eluent (an elution solvent), a flow amount (aflow rate) of 1.0 ml/min, and polystyrene (manufactured by Showa DenkoK.K.) as a standard sample.

For the hydrolysis of alkoxysilyl group, acyloxyalkyl group, orhalogenated silyl group, 0.5 mol to 100 mol, preferably 1 mol to 10 molof water is used per mol of the hydrolysable group.

Furthermore, 0.001 mol to 10 mol, preferably 0.001 mol to 1 mol of ahydrolysis catalyst, may be used per mol of the hydrolysable group.

The reaction temperature at the time of hydrolysis and condensation isnormally 20° C. to 80° C.

The hydrolysis may be either completely or partially performed. That is,a hydrolysis product and a monomer may remain in ahydrolysis-condensation product. A catalyst may be used for thehydrolysis and condensation.

Examples of the hydrolysis catalyst include a metal chelate compound, anorganic acid, an inorganic acid, an organic base, and an inorganic base.

Examples of the metal chelate compound serving as the hydrolysiscatalyst include: titanium chelate compounds, such as triethoxymono(acetylacetonato)titanium, tri-n-propoxymono(acetylacetonato)titanium tri-i-propoxymono(acetylacetonato)titanium, tri-n-butoxymono(acetylacetonato)titanium, tri-sec-butoxymono(acetylacetonato)titanium, tri-t-butoxymono(acetylacetonato)titanium, diethoxy bis(acetylacetonato)titanium,di-n-propoxy bis(acetylacetonato)titanium, di-i-propoxybis(acetylacetonato)titanium, di-n-butoxy bis(acetylacetonato)titanium,di-sec-butoxy bis(acetylacetonato)titanium, di-t-butoxybis(acetylacetonato)titanium, monoethoxy tris(acetylacetonato)titanium,mono-n-propoxy tris(acetylacetonato)titanium, mono-i-propoxytris(acetylacetonato)titanium, mono-n-butoxytris(acetylacetonato)titanium, mono-sec-butoxytris(acetylacetonato)titanium, mono-t-butoxytris(acetylacetonato)titanium, tetrakis(acetylacetonato)titanium,triethoxy mono(ethylacetoacetate)titanium, tri-n-propoxymono(ethylacetoacetate)titanium, mono(ethylacetoacetate)titanium,tri-n-butoxy mono(ethylacetoacetate)titanium, tri-sec-butoxymono(ethylacetoacetate)titanium, tri-t-butoxymono(ethylacetoacetate)titanium, diethoxybis(ethylacetoacetate)titanium, di-n-propoxybis(ethylacetoacetate)titanium, di-i-propoxybis(ethylacetoacetate)titanium, di-n-butoxybis(ethylacetoacetate)titanium, di-sec-butoxybis(ethylacetoacetate)titanium, di-t-butoxybis(ethylacetoacetate)titanium, monoethoxytris(ethylacetoacetate)titanium, mono-n-propoxytris(ethylacetoacetate)titanium, mono-i-propoxytris(ethylacetoacetate)titanium, mono-n-butoxytris(ethylacetoacetate)titanium, mono-sec-butoxytris(ethylacetoacetate)titanium, mono-t-butoxytris(ethylacetoacetate)titanium, tetrakis(ethylacetoacetate)titanium,mono(acetylacetonato)tris(ethylacetoacetate)titanium,bis(acetylacetonato)bis(ethylacetoacetate)titanium, andtris(acetylacetonato)mono(ethylacetoacetate)titanium; zirconium chelatecompounds, such as triethoxy mono(acetylacetonato)zirconium,tri-n-propoxy mono(acetylacetonato)zirconium, tri-i-propoxymono(acetylacetonato)zirconium, tri-n-butoxymono(acetylacetonato)zirconium, tri-sec-butoxymono(acetylacetonato)zirconium, tri-t-butoxymono(acetylacetonato)zirconium, diethoxy bis(acetylacetonato)zirconium,di-n-propoxy bis(acetylacetonato)zirconium, di-i-propoxybis(acetylacetonato)zirconium, di-n-butoxybis(acetylacetonato)zirconium, di-sec-butoxybis(acetylacetonato)zirconium, di-t-butoxybis(acetylacetonato)zirconium, monoethoxytris(acetylacetonato)zirconium, mono-n-propoxytris(acetylacetonato)zirconium, mono-i-propoxytris(acetylacetonato)zirconium, mono-n-butoxytris(acetylacetonato)zirconium, mono-sec-butoxytris(acetylacetonato)zirconium, mono-t-butoxytris(acetylacetonato)zirconium, tetrakis(acetylacetonato)zirconium,triethoxy mono(ethylacetoacetate)zirconium, tri-n-propoxymono(ethylacetoacetate)zirconium, tri-i-propoxymono(ethylacetoacetate)zirconium, tri-n-butoxymono(ethylacetoacetate)zirconium, tri-sec-butoxymono(ethylacetoacetate)zirconium, tri-t-butoxymono(ethylacetoacetate)zirconium, diethoxybis(ethylacetoacetate)zirconium, di-n-propoxybis(ethylacetoacetate)zirconium, di-i-propoxybis(ethylacetoacetate)zirconium, di-n-butoxybis(ethylacetoacetate)zirconium, di-sec-butoxybis(ethylacetoacetate)zirconium, di-t-butoxybis(ethylacetoacetate)zirconium, monoethoxytris(ethylacetoacetate)zirconium, mono-n-propoxytris(ethylacetoacetate)zirconium, mono-i-propoxytris(ethylacetoacetate)zirconium, mono-n-butoxytris(ethylacetoacetate)zirconium, mono-sec-butoxytris(ethylacetoacetate)zirconium mono-t-butoxy tris(ethylacetoacetatee)zirconium, tetrakis(ethylacetoacetate)zirconium,mono(acetylacetonato)tris(ethylacetoacetate)zirconium,bis(acetylacetonato)bis(ethylacetoacetate)zirconium, andtris(acetylacetonato)mono(ethylacetoacetate)zirconium; and aluminumchelate compounds, such as tris(acetylacetonato)aluminum andtris(ethylacetoacetate)aluminum.

Examples of the organic acid serving as the hydrolysis catalyst includeacetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoicacid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid,oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid,gallic acid, butyric acid, mellitic acid, arachidonic 2-ethylhexanoicacid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylicacid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid,benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid,trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid,sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaricacid.

Examples of the inorganic acid serving as the hydrolysis catalystinclude hydrochloric acid, nitric acid, sulfuric acid, hydrofluoricacid, and phosphoric acid.

Examples of the organic base serving as the hydrolysis catalyst includepyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline,trimethylamine, triethylamine, monoethanolamine diethanolamine,dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine,diazabicyclooctane, diazabicyclononane, diazabicycloundecene, andtetraethylammonium hydroxide. Examples of the inorganic base includeammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, andcalcium hydroxide. Among these catalysts, the metal chelate compounds,the organic acids, and the inorganic acids are preferable, and thesecatalysts may be used alone or in combination of two or more kindsthereof.

Examples of the organic solvent used for the hydrolysis include:aliphatic hydrocarbon-based solvents, such as n-pentane, i-pentane,n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane,n-octane, i-octane, cyclohexane, and methylcyclohexane; aromatichydrocarbon-based solvents, such as benzene, toluene, xylene,ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene,i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene,di-i-propylbenzene, n-amylnaphthalene, and trimethylbenzene; monohydricalcohol-based solvents, such as methanol, ethanol, n-propanol,i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol,i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol,n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol,heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol,2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonylalcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol,cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzylalcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; polyhydricalcohol-based solvents, such as ethylene glycol, propylene glycol,1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4,hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol-1,3, diethyleneglycol, dipropylene glycol, triethylene glycol, tripropylene glycol, andglycerol; ketone-based solvents, such as acetone, methyl ethyl ketone,methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone,methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone,methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone,cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone,diacetone alcohol, acetophenone, and fenchone; ether-based solvents,such as ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether,2-ethylhexyl ether, ethylene oxide, 2-propylene oxide, dioxolane,4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethylether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether,ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether,ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutylether, ethylene glycol dibutyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, diethylene glycol diethylether, diethylene glycol mono-n-butyl ether, diethylene glycoldi-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol,tetraethylene glycol di-n-butyl ether, propylene glycol monomethylether, propylene glycol monoethyl ether, propylene glycol monopropylether, propylene glycol monobutyl ether, propylene glycol monomethylether acetate, dipropylene glycol monomethyl ether, dipropylene glycolmonoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycolmonobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran,and 2-methyltetrahydrofuran; ester-based solvents, such as diethylcarbonate, methyl acetate, ethyl acetate, γ-butyrolactone,γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate,i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentylacetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutylacetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate,methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethylacetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycolmonoethyl ether acetate, diethylene glycol monomethyl ether acetate,diethylene glycol monoethyl ether acetate, diethylene glycolmono-n-butyl ether acetate, propylene glycol monomethyl ether acetate,propylene glycol monoethyl ether acetate, propylene glycol monopropylether acetate, propylene glycol monobutyl ether acetate, dipropyleneglycol monomethyl ether acetate, dipropylene glycol monoethyl etheracetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate,n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyloxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate,diethyl malonate, dimethyl phthalate, and diethyl phthalate;nitrogen-containing solvents, such as N-methylformamide,N,N-dimethylformamide, N,N-diethylformamide, acetamide,N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide,N-methylpyrrolidone (NMP); and sulfur-containing solvents, such asdimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene,dimethyl sulfoxide, sulfolane, and 1,3-propanesultone. These solventsmay be used alone or in combination of two or more kinds thereof.

In particular, ketone-based solvents, such as acetone, methyl ethylketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone,methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone,methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone,cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone,diacetone alcohol, acetophenone, and fenchone, are preferable in termsof the preservation stability of the solutions.

Furthermore, bisphenol S or a bisphenol S derivative may be added as anadditive. The amount of bisphenol S or a bisphenol S derivative added is0.01 part by mass to 20 parts by mass, 0.01 part by mass to 10 parts bymass, or 0.01 part by mass to 5 parts by mass with respect to 100 partsby mass of polyorganosiloxane.

Preferable examples of the bisphenol S and the bisphenol S derivativeare as follows.

The resist underlayer film-forming composition of the present inventionmay include a curing catalyst. The curing catalyst acts as a curingcatalyst when a coating film containing polyorganosiloxane formed from ahydrolysis-condensation product is heated and cured.

As the curing catalyst, ammonium salts, phosphines, phosphonium salts,and sulfonium salts may be used.

Examples of the ammonium salts include: a quaternary ammonium salthaving a structure of Formula (D-1):

(where m is an integer of 2 to 11; n₁ is an integer of 2 to 3; R²¹ is analkyl group or an aryl group; and Y_(A) ⁻ is an anion);

a quaternary ammonium salt having a structure of Formula (D-2):R²²R²³R²⁴R²⁵N⁺Y_(A) ⁻  Formula (D-2)(where each of R²², R²³, R²⁴, and R²⁵ is an alkyl group or an arylgroup; N is a nitrogen atom; Y_(A) ⁻ is an anion; and each of R²², R²³,R²⁴, and R²⁵ is bonded to the nitrogen atom through a C—N bond);

a quaternary ammonium salt having a structure of Formula (D-3):

(where each of R²⁶ and R²⁷ is an alkyl group or an aryl group; and Y_(A)⁻ is an anion);

a quaternary ammonium salt having a structure of Formula (D-4):

(where R²⁸ is an alkyl group or an aryl group; and Y_(A) ⁻ is an anion);

a quaternary ammonium salt having a structure of Formula (D-5):

(where each of R²⁹ and R³⁰ is an alkyl group or an aryl group; and Y_(A)⁻ is an anion); and

a tertiary ammonium salt having a structure of Formula (D-6):

(where in is an integer of 2 to 11; n₁ is an integer of 2 to 3; H is ahydrogen atom; and Y_(A) ⁻ is an anion).

Examples of the phosphonium salts include a quaternary phosphonium saltof Formula (D-7):R³¹R³²R³³R³⁴P⁺Y_(A) ⁻  Formula (D-7)(where each of R³¹, R³², R³³, and R³⁴ is an alkyl group or an arylgroup; P is a phosphorus atom; Y_(A) ⁻ is an anion; and each of R³¹,R³², R³³, and R³⁴ is bonded to the phosphorus atom through a C—P bond).

Examples of the sulfonium salts include a tertiary sulfonium salt ofFormula (D-8):R³⁵R³⁶R³⁷S⁺Y_(A) ⁻  Formula (D-8)(where each of R³⁵, R³⁶, and R³⁷ is an alkyl group or an aryl group; Sis a sulfur atom; Y_(A) ⁻ is an anion; and each of R³⁵, R³⁶, and R³⁷ isbonded to the sulfur atom through a C—S bond).

The compound of Formula (D-1) above is a quaternary ammonium saltderived from an amine, and, in Formula (D-1), m is an integer of 2 to 11and n₁ is an integer of 2 to 3. R²¹ of this quarternary ammonium salt isa C₁₋₁₈, preferably C₂₋₁₀ alkyl or aryl group. Examples of R²¹ includelinear alkyl groups, such as ethyl, propyl and butyl groups, benzylgroup, cyclohexyl group, cyclohexylmethyl group, and dicyclopentadienylgroup. Examples of the anion (Y_(A) ⁻) include: halide ions, such aschloride ion (Cl⁻), bromide ion (Br⁻), and iodide ion (I⁻); and acidgroups, such as carboxylate (—COO⁻), sulfonato (—SO₃ ⁻), and alcoholate(—O⁻).

The compound of Formula (D-2) above is a quarternary ammonium salthaving a structure of R²²R²³R²⁴R²⁵N⁺Y_(A) ⁻. Each of R²², R²³, R²⁴, andR²⁵ of this quarternary ammonium salt is a C₁₋₁₈ alkyl or aryl group, ora silane compound bonded to a silicon atom through a Si—C bond. Examplesof the anion (Y_(A) ⁻) include: halide ions, such as chloride ion (Cl⁻),bromide ion (Br⁻), and iodide ion (I⁻); and acid groups, such ascarboxylate (—COO⁻), sulfonato (—SO₃ ⁻), and alcoholate (—O⁻). Thisquarternary ammonium salt is commercially available, and examples ofthis quarternary ammonium salt include tetramethylammonium acetate,tetrabutylammonium acetate, benzyltriethylammonium chloride,benzyltriethylammonium bromide, methyltrioctylammonium chloride,benzyltributylammonium chloride, and benzyltrimethylammonium chloride.

The compound of Formula (D-3) is a quarternary ammonium salt derivedfrom a 1-substituted imidazole, and, in Formula (D-3), each of R²⁶ andR²⁷ is a C₁₋₁₈ alkyl or aryl group, and the sum total of the number ofcarbon atoms of R²⁶ and R²⁷ is preferably 7 or more. Examples of R²⁶include methyl group, ethyl group, propyl group, phenyl group, andbenzyl group. Examples of R²⁷ include benzyl group, octyl group, andoctadecyl group. Examples of the anion (Y_(A) ⁻) include: halide ions,such as chloride ion (Cl⁻), bromide ion (Br⁻), and iodide ion (I⁻); andacid groups, such as carboxylate (—COO⁻), sulfonato (—SO₃ ⁻), andalcoholate (—O⁻). Although this compound is commercially available, thecompound can be produced, for example, by a reaction between animidazole-based compound, such as 1-methylimidazole or1-benzylimidazole, and an alkyl halide or an aryl halide, such as benzylbromide or methyl bromide.

The compound of Formula (D-4) above is a quarternary ammonium saltderived from pyridine, and in Formula (D-4), R²⁸ is a C₁₋₁₈, preferablyC₄₋₁₈ alkyl or aryl group, and examples of R²⁸ include butyl group,octyl group, benzyl group, and lauryl group. Examples of the anion(Y_(A) ⁻) include: halide ions, such as chloride ion (Cl⁻), bromide ion(Br⁻), and iodide ion (I⁻); and acid groups, such as carboxylate(—COO⁻), sulfonato (—SO₃ ⁻), and alcoholate (—O⁻). Although thiscompound is commercially available, the compound can be produced, forexample, by a reaction between pyridine and an alkyl halide or an arylhalide, such as lauryl chloride, benzyl chloride, benzyl bromide, methylbromide, or octyl bromide. Examples of this compound includeN-laurylpyridinium chloride and N-benzylpyridinium bromide.

The compound of Formula (D-5) above is a quarternary ammonium saltderived from a substituted pyridine, represented by picoline, and inFormula (D-5), R²⁹ is a C₁₋₁₈, preferably C₄₋₁₈ alkyl or aryl group, andexamples of R²⁹ include methyl group, octyl group, lauryl group, andbenzyl group. R³⁰ is a C₁₋₁₈ alkyl or aryl group, and, when the compoundis, for example, a quarternary ammonium salt derived from picoline, R³⁰is a methyl group. Examples of the anion (Y_(A) ⁻) include: halide ions,such as chloride ion (Cl⁻), bromide ion (Br⁻), and iodide ion (I⁻); andacid groups, such as carboxylate (—COO⁻), sulfonato (—SO₃ ⁻), andalcoholate (—O⁻). Although this compound is commercially available, thecompound can be produced, for example, by a reaction between asubstituted pyridine, such as picoline, and an alkyl halide or an arylhalide, such as methyl bromide, octyl bromide, lauryl chloride, benzylchloride, or benzyl bromide. Examples of this compound includeN-benzylpicolinium chloride, N-benzylpicolinium bromide, andN-laurylpicolinium chloride.

The compound of Formula (D-6) is a tertiary ammonium salt derived froman amine, and, in Formula (D-6), m is an integer of 2 to 11 and n₁ is aninteger of 2 to 3. Examples of the anion (Y_(A) ⁻) include: halide ions,such as chloride ion (Cl⁻), bromide ion (Br⁻), and iodide ion (I⁻); andacid groups, such as carboxylate (—COO⁻), sulfonato (—SO₃ ⁻), andalcoholate (—O⁻). The compound can be produced, for example, by areaction between an amine and a weak acid, such as carboxylic acid orphenol. Examples of the carboxylic acid include formic acid and aceticacid. In the case of using formic acid, the anion (Y_(A) ⁻) is (HCOO⁻).In the case of using acetic acid, the anion (Y_(A) ⁻) is (CH₃COO⁻).Alternatively, in the case of using phenol, the anion (Y_(A) ⁻) is(C₆H₅O⁻).

The compound of Formula (D-7) above is a quaternary phosphonium salthaving a structure of R³¹, R³², R³³, R³⁴P⁺Y_(A) ⁻. Each of R³¹, R³²,R³³, and R³⁴ is a C₁₋₁₈ alkyl or aryl group, or a silane compound bondedto a silicon atom through a Si—C bond. Three of the four substituents,R³¹ to R³⁴, are preferably a phenyl group or a substituted phenyl group,and examples of the substituents include phenyl group and tolyl group.The remaining one substituent is a C₁₋₁₈ alkyl or aryl group, or asilane compound bonded to a silicon atom through a Si—C bond. Examplesof the anion N_(A) ⁻) include: halide ions, such as chloride ion (Cl⁻),bromide ion (Br⁻), and iodide ion (I⁻); and acid groups, such ascarboxylate (—COO⁻), sulfonato (—SO₃ ⁻), and alcoholate (—O⁻). Thiscompound is commercially available, and examples of the compoundinclude: tetraalkylphosphonium halides, such as tetra-n-butylphosphoniumhalides and tetra-n-propylphosphonium halides; trialkylbenzylphosphoniumhalides, such as triethylbenzylphosphonium halides;triphenylmonoalkylphosphonium halides, such astriphenylmethylphosphonium halides and triphenylethylphosphoniumhalides; triphenylbenzylphosphonium halides; tetraphenylphosphoniumhalides; tritolylmonoarylphosphonium halides; andtritolylmonoalkylphosphonium halides (in which a halogen atom is achlorine atom or a bromine atom). In particular,triphenylmonoalkylphosphonium halides, such astriphenylmethylphosphonium halides and triphenylethylphosphoniumhalides; triphenylmonoarylphosphonium halides, such astriphenylbenzylphosphonium halides; tritolyimonoarylphosphonium halides,such as tritolylmonophenylphosphonium halides; andtritolylmonoalkylphosphonium halides, such astritolylmonomethylphosphonium halides (in which a halogen atom is achlorine atom or a bromine atom), are preferable.

Examples of the phosphines include: primary phosphines, such asmethylphosphine, ethylphosphine, propylphosphine, isopropylphosphine,isobutylphosphine, and phenylphosphine; secondary phosphines, such asdimethylphosphine, diethylphosphine, diisopropylphosphine,diisoamylphosphine, and diphenylphosphine; and tertiary phosphines, suchas trimethylphosphine, triethylphosphine, triphenylphosphine,methyldiphenylphosphine, and dimethylphenylphosphine.

The compound of Formula (D-8) above is a tertiary sulfonium salt havinga structure of R³⁵R³⁶R³⁷S⁺Y_(A) ⁻. Each of R³⁵, R³⁶, and R³⁷ is a C₁₋₁₈alkyl or aryl group, or a silane compound bonded to a silicon atomthrough a Si—C bond. Three of the four substituents, R³⁵ to R³⁷, arepreferably a phenyl group or a substituted phenyl group, and examples ofthe substituents include phenyl group and tolyl group. The remaining onesubstituent is a C₁₋₁₈ alkyl or aryl group. Examples of the anion (Y_(A)⁻) include: halide ions, such as chloride ion (Cl⁻), bromide ion (Br⁻),and iodide ion (I⁻); and acid groups, such as carboxylate (—COO⁻),sulfonato (—SO₃ ⁻), alcoholate (—O⁻), maleic acid anion, and nitric acidanion.

This compound is commercially available, and examples of the compoundinclude: tetraalkylsulfonium halides, such as tri-n-butylsulfoniumhalides and tri-n-propylsulfonium halides; trialkylbenzylsulfoniumhalides, such as diethylbenzylsulfonium halides;diphenylmonoalkylsulfonium halides, such as diphenylmethylsulfoniumhalides and diphenylethylsulfonium halides; tetraalkylphosphoniumcarboxylates, such as triphenyl sulfonium halides (in which a halogenatom is a chlorine atom or the bromine atom), tri-n-butylsulfoniumcarboxylate, and tri-n-propylsulfonium carboxylate;trialkylbenzylsulfonium carboxylates, such as diethylbenzylsulfoniumcarboxylate; diphenylmonoalkylsulfonium carboxylates, such asdiphenylmethylsulfonium carboxylate and diphenylethylsulfoniumcarboxylate; and triphenylsulfonium carboxylate. Triphenylsulfoniumhalides and triphenylsulfonium carboxylate may be preferably used.

Furthermore, in the present invention, a nitrogen-containing silanecompound may be added as a curing catalyst. Examples of thenitrogen-containing silane compound include an imidazole-ring-containingsilane compound, such asN-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

The amount of the curing catalyst added is 0.01 part by mass to 10 partsby mass, 0.01 part by mass to 5 parts by mass, or 0.01 part by mass to 3parts by mass, with respect to 100 parts by mass of polyorganosiloxane.

A hydrolyzable silane is hydrolyzed and condensed using a catalyst in asolvent, and alcohol as a by-product, the used hydrolysis catalyst, andwater can be removed from an obtained hydrolysis-condensation product (apolymer) at the same time, for example, by distillation under reducedpressure. Furthermore, an acid catalyst or a base catalyst used in thehydrolysis can be removed by neutralization or ion exchange. In theresist underlayer film-forming composition for lithography of thepresent invention, an organic acid, water, and alcohol, or a combinationthereof may be added for the purpose of stabilizing the resistunderlayer film-forming composition including thehydrolysis-condensation product.

Examples of the organic acid include oxalic acid, malonic acid,methylmalonic acid, succinic acid, maleic acid, malic acid, tartaricacid, phthalic acid, citric acid, glutaric acid, citric acid, lacticacid, and salicylic acid. Among these, oxalic acid, maleic acid and thelike are preferable. The amount of the organic acid added is 0.1 part bymass to 5.0 parts by mass with respect to 100 parts by mass of acondensation product (polyorganosiloxane). Furthermore, pure water,ultrapure water, and ion exchange water may be used as the water to beadded, and the amount of the water added may be 1 part by mass to 20parts by mass with respect to 100 parts by mass of the resist underlayerfilm-forming composition.

As the alcohol to be added, alcohol that easily vaporizes with heatingafter the application is preferable, and examples of this alcoholinclude methanol, ethanol, propanol, isopropanol (2-propanol), andbutanol. The amount of the alcohol added may be 1 part by mass to 20parts by mass with respect to 100 parts by mass of the resist underlayerfilm-forming composition.

Besides the above-mentioned components, the underlayer film-formingcomposition for lithography of the present invention may include anorganic polymer compound, a photoacid generator, and a surfactant, asnecessary.

The use of an organic polymer compound allows the adjustment of the dryetching rate (the amount of reduction in film thickness per unit time),the attenuation coefficient, the refractive index and the like of aresist underlayer film formed from the underlayer film-formingcomposition for lithography of the present invention.

The organic polymer compound is not limited to a particular compound,and various kinds of organic polymers may be used. For example,polycondensation polymers and addition polymerization polymers may beused. Examples of the addition polymerization polymers andpolycondensation polymers to be used include polyesters, polystyrenes,polyimides, acrylic polymers, methacrylic polymers, polyvinyl ethers,phenol novolacs, naphthol novolacs, polyethers, polyamides, andpolycarbonates. Organic polymers having aromatic ring structures actingas an absorption site, such as a benzene ring, a naphthalene ring, ananthracene ring, a triazine ring, a quinoline ring, and a quinoxalinering, are preferably used.

Examples of the organic polymer compound include: additionpolymerization polymers including, as a structural unit thereof,addition polymerizable monomers, such as benzyl acrylate, benzylmethacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate,anthrylmethyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether,and N-phenylmaleimide; and polycondensation polymers, such as phenolnovolacs and naphthol novolacs.

In the case Where an addition polymerization polymer is used as theorganic polymer compound, the polymer compound may be a homopolymer or acopolymer. For the manufacture of the addition polymerization polymer,an addition polymerizable monomer is used. Examples of the additionpolymerizable monomer include acrylic acid, methacrylic acid, an acrylicester compound, a methacrylic ester compound, an acrylamide compound, amethacrylamide compound, a vinyl compound, a styrene compound, amaleimide compound, a maleic anhydride, and acrylonitrile.

Examples of the acrylic ester compound include methyl acrylate, ethylacrylate, normal hexyl acrylate, isopropyl acrylate, cyclohexylacrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl acrylate,2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate,2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate,2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutylacrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate,2-methyl-2-adamantyl acrylate,5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone,3-acryloxypropyltriethoxysilane, and glycidyl acrylate.

Examples of the methacrylic ester compound include methyl methacrylate,ethyl methacrylate, normal hexyl methacrylate, isopropyl methacrylate,cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate,anthrylmethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropylmethacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethylmethacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate,2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate,2-methyl-2-adamantyl methacrylate,5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone,3-methacryloxypropyltriethoxysilane, glycidyl methacrylate,2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenylmethacrylate.

Examples of the acrylamide compound include acrylamide,N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide,N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.

Examples of the methacrylamide compound include methacrylamide,N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide,N-phenylmethacrylamide, N,N-dimethylmethacrylamide, andN-anthrylacrylamide.

Examples of the vinyl compound include vinyl alcohol, 2-hydroxyethylvinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether,vinylacetic acid, vinyl trimethoxy silane, 2-chloroethyl vinyl ether,2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene.

Examples of the styrene compound include styrene, hydroxystyrene,chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, andacetylstyrene.

Examples of the maleimide compound include maleimide, N-methylmaleimide,N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, andN-hydroxyethylmaleimide.

In the case of using a polycondensation polymer as the polymer, examplesof the polymer include a polycondensation polymer of a glycol compoundand a dicarboxylic acid compound. Examples of the glycol compoundinclude diethylene glycol, hexamethylene glycol, and butylene glycol.Examples of the dicarboxylic acid compound include succinic acid, adipicacid, terephthalic acid, and maleic anhydride. Examples of thepolycondensation polymer include polyesters, polyamides, and polyimides,such as poly(pyromellitic imide), poly(p-phenyleneterephthalamide),poly(butylene terephthalate), and poly(ethylene terephthalate).

In the case where the organic polymer compound has a hydroxy group, thishydroxy group can cause a crosslinking reaction with apolyorganosiloxane. As the organic polymer compound, a polymer compoundhaving a weight-average molecular weight of, for example, 1,000 to1,000,000, 3,000 to 300,000, 5,000 to 200,000, or 10,000 to 100,000 maybe used.

The organic polymer compounds may be used alone, or in combination oftwo or more kinds thereof.

In the case of using the organic polymer compound, the amount of theorganic polymer compound is 1 part by mass to 200 parts by mass, 5 partsby mass to 100 parts by mass, 10 parts by mass to 50 parts by mass, or20 parts by mass to 30 parts by mass with respect to 100 parts by massof a polycondensate (polyorganosiloxane).

The resist underlayer film-forming composition of the present inventionmay include an acid generator. Examples of the acid generator includethermal acid generators and photoacid generators.

Photoacid generators generate an acid at the time of the light exposureof the resist. Accordingly, the acidity of an underlayer film can beadjusted. This is one method for adjusting the acidity of an underlayerfilm to the acidity of a resist serving as an upper layer. Furthermore,the adjustment of acidity of an underlayer film allows the pattern shapeof a resist formed as the upper layer to be adjusted.

Examples of the photoacid generator included in the resist underlayerfilm-forming composition of the present invention include an onium saltcompound, a sulfonimide compound, and a disulfonyldiazomethane compound.

Examples of the onium salt compound include: iodonium salt compounds,such as diphenyliodonium hexafluorophosphate, diphenyliodoniumtrifluoromethanesulfonate, diphenyliodonium nonafluoro normalbutanesulfonate, diphenyliodonium perfluoro normal octanesulfonate,diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodoniumcamphorsulfonate, and bis(4-tert-butylphenyl)iodoniumtrifluoromethanesulfonate; and sulfonium salt compounds, such astriphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, andtriphenylsulfonium trifluoromethanesulfonate.

Examples of the sulfonimide compound includeN-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro normal butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, andN-(trifluoromethanesulfonyloxy)naphthalimide.

Examples of the disulfonyldiazomethane compound includebis(trifluoromethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane,bis(p-toluenesulfonyl)diazomethane,bis(2,4-dimethylbenzenesulfonyl)diazomethane, andmethylsulfonyl-p-toluenesulfonyldiazomethane.

The photoacid generators may be used alone, or in combination of two ormore kinds thereof.

In the case of using the photoacid generator, the amount of thephotoacid generator is 0.01 part by mass to 5 parts by mass, 0.1 part bymass to 3 parts by mass, or 0.5 part by mass to 1 part by mass, withrespect to 100 parts by mass of a polycondensation product(polyorganosiloxane).

Surfactants effectively suppress the formation of pinholes, striationsand the like when the resist underlayer film-forming composition forlithography of the present invention is applied to a substrate.

Examples of a surfactant included in the resist underlayer film-formingcomposition of the present invention include: nonionic surfactants, suchas polyoxyethylene alkyl ethers including polyoxyethylene lauryl ethers,polyoxyethylene stearyl ethers, polyoxyethylene cetyl ethers, andpolyoxyethylene oleyl ethers, polyoxyethylene alkylallyl ethers,including polyoxyethylene octylphenol ethers and polyoxyethylenenonylphenol ethers, polyoxyethylene-polyoxypropylene block copolymers,sorbitan fatty acid esters, including sorbitan monolaurates, sorbitanmonopalmitates, sorbitan monostearates, sorbitan monooleates, sorbitantrioleates, and sorbitan tristearates, polyoxyethylene sorbitan fattyacid esters, including polyoxyethylene sorbitan monolaurates,polyoxyethylene sorbitan monopalmitates, polyoxyethylene sorbitanmonostearates, polyoxyethylene sorbitan trioleates, and polyoxyethylenesorbitan tristearates; fluorine-based surfactants, such as the tradenames EFTOP EF301, EF303, and EF352 (manufactured by Tohkem ProductsCorporation), the trade names MEGAFAC F171, F173, R-08, R-30, R-30N, andR-40LM (manufactured by DIC Corporation), Fluorad FC430 and FC431(manufactured by Sumitomo 3M Limited), the trade name Asahi Guard AG710and the trade names SURFLON S-382, SC101, SC102, SC1.03, SC104, SC105,and SC106 (manufactured by Asahi Glass Co., Ltd.); and an organosiloxanepolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). Thesesurfactants may be used alone, or in combination of two or more kindsthereof. In the case of using the surfactant, the amount of thesurfactant is 0.0001 part by mass to 5 parts by mass, 0.001 part by massto 1 part by mass, or 0.01 part by mass to 1 part by mass with respectto 100 parts by mass of a polycondensation product (polyorganosiloxane).

Furthermore, to the resist underlayer film forming composition of thepresent invention, a rheology controlling agent and an adhesionassistant may be added. A rheology controlling agent effectivelyimproves the fluidity of the underlayer film-forming composition. Anadhesion assistant effectively improves adhesion between a semiconductorsubstrate or a resist and an underlayer film.

As the solvent used for the resist underlayer film-forming compositionof the present invention, a solvent capable of dissolving theabove-mentioned solid contents may be used without particularlimitations. Examples of the solvent include methylcellosolve acetate,ethylcellosolve acetate, propylene glycol, propylene glycol monomethylether, propylene glycol monoethyl ether, methyl isobutyl carbinol,propylene glycol monobutyl ether, propylene glycol monomethyl etheracetate, propylene glycol monoethyl ether acetate, propylene glycolmonopropyl ether acetate, propylene glycol monobutyl ether acetate,toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone,ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethylethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate,methyl 3-methoxypropinoate, ethyl 3-methoxypropionate, ethyl3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethylpyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethylether, ethylene glycol monopropyl ether, ethylene glycol monobutylether, ethylene glycol monomethyl ether acetate, ethylene glycolmooethyl ether acetate, ethylene glycol monopropyl ether acetate,ethylene glycol monobutyl ether acetate, diethylene glycol dimethylether, diethylene glycol diethyl ether, diethylene glycol dipropylether, diethylene glycol dibutyl ether, propylene glycol monomethylether, propylene glycol dimethyl ether, propylene glycol diethyl ether,propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyllactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyllactate, methyl formate, ethyl formate, propyl formate, isopropylformate, butyl formate, isobutyl formate, amyl formate, isoamyl formate,methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexylacetate, methyl propionate, ethyl propionate, propyl propionate,isopropyl propionate, butyl propionate, isobutyl propionate, methylbutyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butylbutyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate,methyl 2-hydroxy-3-methybutyrate, ethyl methoxyacetate, ethylethoxyacetate, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate,ethyl 3-methoxy propionate, 3-methoxybutyl acetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate,toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butylketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone,N,N-dimethylformamide. N-methylacetamide, N,N-dimethylacetamide,N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. Thesesolvents may be used alone, or in combination of two or more kindsthereof.

Hereinafter, the use of the resist underlayer film-forming compositionof the present invention is described.

A resist underlayer film is formed by applying the resist underlayerfilm-forming composition of the present invention onto a substrate, oris formed by applying the resist underlayer film-forming compositiononto a substrate via an organic underlayer film, and a resist film (forexample, photoresist or electron resist) is formed on the resistunderlayer film. Then, a resist pattern is formed by light exposure anddevelopment. Using the resist pattern, the resist underlayer film isdry-etched to perform the transfer of the pattern, and the substrate isprocessed using the pattern, or the organic underlayer film is etched toperform the transfer of the pattern and the substrate is processed usingthe organic underlayer film.

In the formation of a fine pattern, the film thickness of a resist tendsto be made thinner for the purpose of preventing pattern collapse. Dueto such a thinner resist film, the etching rate of dry etching fortransferring a pattern to a film present under the resist film needs tobe higher than that of dry etching of the upper layer film in order toperform the pattern transfer. In the present invention, a resistunderlayer film (containing an inorganic silicon-based compound) of thepresent invention is coated on a substrate via an organic underlayerfilm or not via an organic underlayer film, and a resist film (anorganic resist film) is coated thereon in this order. Depending on aselected etching gas, a film of an organic component and a film of aninorganic component considerably differ in dry etching rate. With theuse of an oxygen-based gas, a film of an organic component is dry-etchedat a higher rate. In contrast, with the use of a halogen-containing gas,a film of an inorganic component is dry-etched at a higher rate.

For example, a resist pattern is formed, then a resist underlayer filmof the present invention present under a layer with the resist patternis dry-etched using a halogen-containing gas to transfer the pattern tothe resist underlayer film, and, using the pattern transferred to theresist underlayer film, a substrate is processed with ahalogen-containing gas. Alternatively, using a resist underlayer film towhich the pattern is transferred, an organic underlayer film under theresist underlayer film is dry-etched by an oxygen-based gas to transferthe pattern to the organic underlayer film, and, using the organicunderlayer film to which the pattern is transferred, a substrate isprocessed with a halogen-containing gas.

Here, onto a substrate used for the manufacture of a semiconductordevice (for example, a silicon wafer substrate, asilicon/silicon-dioxide coated substrate, a silicon nitride substrate, aglass substrate, an ITO substrate, a polyimide substrate, or a lowdielectric constant material (low-k material) coated substrate), theresist underlayer film-forming composition of the present invention isapplied by appropriate application means, such as a spinner and acoater, followed by baking to form a resist underlayer film. The bakingis performed under the conditions appropriately selected from heatingtemperatures of 80° C. to 250° C. and heating duration of 0.3 minute to60 minutes. The baking temperature is preferably 150° C. to 250° C., andthe heating duration is preferably 0.5 minute to 2 minutes. Here, thethickness of the underlayer film formed is, for example, 10 nm to 1,000nm, 20 nm to 500 nm, 50 nm to 300 nm, or 100 nm to 200 nm.

Next, a photoresist layer, for example, is formed on the resistunderlayer film. The photoresist layer can be formed by a well-knownprocess, that is, the application of a solution of a photoresistcomposition onto the underlayer film, followed by baking. The filmthickness of the photoresist layer is, for example, 50 nm to 10,000 nm,100 nm to 2,000 nm, or 200 nm to 1,000 nm.

In the present invention, an organic underlayer film can be formed on asubstrate, the resist underlayer film of the present invention can thenbe formed on the organic underlayer film, and furthermore, a photoresistcan be coated on the resist underlayer film. This allows the patternwidth of the photoresist to be narrower, and accordingly, even when thephotoresist is applied thinly for the purpose of preventing patterncollapse, substrate processing is made possible by selecting anappropriate etching gas. For example, the use of a fluorine-based gas asart etching gas, which results in a significantly high etching rate fora photoresist, allows the resist underlayer film of the presentinvention to be processed. In contrast, the use of an oxygen-based gasas an etching gas, which results in a significantly high etching ratefor the resist underlayer film of the present invention, allows anorganic underlayer film to be processed. Furthermore, the use of afluorine-based gas as an etching gas, which results in a significantlyhigh rate for the organic underlayer film, allows a substrate to beprocessed.

The photoresist formed on the resist underlayer film of the presentinvention is not limited to a particular one as long as the photoresistis sensitive to light used for exposure. Negative and positivephotoresists may both be used. Examples of the photoresist include apositive photoresist formed of a novolac resin and a 1,2-naphthoquinonediazide sulfonic acid ester; a chemically amplified photoresist formedof a photoacid generator and a binder having a group that is decomposedby acid to increase an alkali dissolution rate; a chemically amplifiedphotoresist formed of an alkali-soluble binder, a photoacid generator,and a low molecular weight compound that is decomposed by acid toincrease an alkali dissolution rate of the photoresist; and a chemicallyamplified photoresist formed of a binder having a group that isdecomposed by acid to increase an alkali dissolution rate, a lowmolecular weight compound that is decomposed by acid to increase analkali dissolution rate of the photoresist, and a photoacid generator.Examples of the photoresists include the trade name APEX-E, manufacturedby Shipley, the trade name PAR710, manufactured by Sumitomo ChemicalCompany, Limited, and the trade name SEPR430, manufactured by Shin-EtsuChemical Co., Ltd. Furthermore, examples of the photoresists includefluorine-atom-containing polymer-based photoresists described in Proc.SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000),and Proc. SPIE, Vol. 3999, 365-374 (2000).

Next, light exposure is performed through a predetermined mask. For thelight exposure, for example, a KrF excimer laser (with a wavelength of248 nm), an ArF excimer laser (with a wavelength of 193 nm), or an F2excimer laser (with a wavelength of 157 nm can be used. After the lightexposure, post exposure bake may be performed, if necessary. The postexposure bake is performed under the conditions appropriately selectedfrom heating temperatures of 70° C. to 150° C. and heating duration of0.3 minute to 10 minutes.

In the present invention, a resist for electron beam lithography or aresist for EUV lithography may be used as a resist in place of aphotoresist. Positive and negative electron beam resists may both beused. Examples of the electron beam resists include a chemicallyamplified resist formed of an acid generator and a binder having a groupthat is decomposed by acid to change an alkali dissolution rate; achemically amplified resist formed of an alkali-soluble binder, an acidgenerator, and a low molecular weight compound that is decomposed byacid to change an alkali dissolution rate of the resist; a chemicallyamplified resist formed of an acid generator, a binder having a groupthat is decomposed by acid to change an alkali dissolution rate, and alow molecular weight compound that is decomposed by acid to change analkali dissolution rate; a non-chemically amplified resist formed of abinder having a group that is decomposed by an electron beam to changean alkali dissolution rate of the resist; and a non-chemically amplifiedresist formed of a binder having a portion that is cut by an electronbeam to change an alkali dissolution rate. Also, in the cases of usingthese electron beam resists, a resist pattern can be formed using anelectron beam as an irradiation source in the same manner as in the caseof using a photoresist.

As the EUV resist, a methacrylate resin-based photoresist may be used.

Next, development is performed using a developing solution (for example,an alkaline developing solution). Thus, for example, in the case ofusing a positive photoresist, an exposed portion of the photoresist isremoved to form a pattern of the photoresist.

Examples of the developing solution include alkaline developingsolutions, such as: aqueous solutions of an alkali metal hydroxide, suchas potassium hydroxide and sodium hydroxide; aqueous solutions of aquaternary ammonium hydroxide, such as tetramethyl ammonium hydroxide,tetraethyl ammonium hydroxide, and choline; and aqueous solutions ofamine, such as ethanolamine, propylamine, and ethylenediamine.Furthermore, a surfactant or other substances may be added to thesedeveloping solutions. The development conditions are appropriatelyselected from temperatures of 5° C. to 50° C. and duration of 10 secondsto 600 seconds.

Furthermore, in the present invention, an organic solvent may be used asa developing solution. After the light exposure, development isperformed using a developing solution (a solvent). Thus, for example, inthe case of using a positive photoresist, an unexposed portion of thephotoresist is removed to form a pattern of the photoresist.

Examples of the developing solution include methyl acetate, butylacetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamylacetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycolmonomethyl ether acetate, ethylene glycol monoethyl ether acetate,ethylene glycol monopropyl ether acetate, ethylene glycol monobutylether acetate, ethylene glycol monophenyl ether acetate, diethyleneglycol monomethyl ether acetate, diethylene glycol monopropyl etheracetate, diethylene glycol monoethyl ether acetate, diethylene glycolmonophenyl ether acetate, diethylene glycol monobutyl ether acetate,2-methoxy butyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate,3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate,propylene glycol monoethyl ether acetate, propylene glycol monopropylether acetate, 2-ethoxy butyl acetate, 4-ethoxy butyl acetate, 4-propoxybutyl acetate, 2-methoxy pentyl acetate, 3-methoxy pentyl acetate,4-methoxy pentyl acetate, 2-methyl-3-methoxy pentyl acetate,3-methyl-3-methoxy pentyl acetate, 3-methyl-4-methoxy pentyl acetate,4-methyl-4-methoxy pentyl acetate, propylene glycol diacetate, methylformate, ethyl formate, butyl formate, propyl formate, ethyl lactate,butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butylcarbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butylpyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate,ethyl propionate, propyl propionate, isopropyl propionate, methyl2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxy propionate, ethyl-3-ethoxy propionate, andpropyl-3-methoxy propionate. Furthermore, a surfactant or othersubstances may be added to these developing solutions. The developmentconditions are appropriately selected from temperatures of 5° C. to 50°C. and duration of 10 seconds to 600 seconds.

Then, using the thus-formed pattern of the photoresist (upper layer) asa protective film, the resist underlayer film (intermediate layer) ofthe present invention is removed. Subsequently, using a film formed ofthe patterned photoresist and the patterned resist underlayer film(intermediate layer) of the present invention as protective films, anorganic underlayer film (lower layer) is removed. Finally, using thepatterned resist underlayer film (intermediate layer) of the presentinvention and the patterned organic underlayer film (lower layer) asprotective films, a semiconductor substrate is processed.

First, a photoresist-removed portion of the resist underlayer film(intermediate layer) of the present invention is removed by dry etchingto make a semiconductor substrate exposed. For the dry etching of theresist underlayer film of the present invention, gases, such astetrafluoromethane (CF₄), pa fluorocyclobutane (C₄F₈), parfluoropropane(C₃F₈), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen,sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorinetrifluoride, chlorine, trichloroborane, and dichloroborane may be used.For the dry etching of the resist underlayer film, a halogen-based gasis preferably used. With dry etching using a halogen-based gas, aphotoresist formed of an organic substance is basically hard to remove.In contrast, the resist underlayer film of the present invention thatcontains many silicon atoms is promptly removed by a halogen-based gas.Thus, a reduction in the film thickness of the photoresist that isassociated with the dry etching of the resist underlayer film can besuppressed. As a result, a thinner photoresist film can be used. The dryetching of the resist underlayer film is preferably performed using afluorine-based gas. Examples of the fluorine-based gas includetetrafluoromethane (CF₄), parfluorocyclobutane (C₄F₈), parfluoropropane(C₃F₈), trifluoromethane, and difluoromethane (CH₂F₂).

After that, using a film formed of the patterned photoresist and thepatterned resist underlayer film of the present invention as protectivefilms, the organic underlayer film is removed. The dry etching of theorganic underlayer film (lower layer) is preferably performed using anoxygen-based gas. This is because the resist underlayer film of thepresent invention that contains many silicon atoms is hard to remove bydry etching using an oxygen-based gas.

Finally, a semiconductor substrate is processed. The processing of thesemiconductor substrate is preferably performed by dry etching using afluorine-based gas.

Examples of the fluorine-based gas include tetrafluoromethane (CF₄),parfluorocyclobutane (C₄F₈), parfluoropropane (C₃F₈), trifluoromethane,and difluoromethane (CH₂F₂).

Furthermore, on the resist underlayer film of the present invention, anorganic anti-reflective coating may be formed before the formation of aphotoresist. An anti-reflective coating composition used for theanti-reflective coating is not limited to a particular one, and may beappropriately selected from various anti-reflective coating compositionsthat have been commonly used for lithography process. Furthermore, theanti-reflective coating may be formed using a common method, forexample, application with a spinner and a coater and baking.

The substrate to which the resist underlayer film-forming composition ofthe present invention is applied may have an organic or inorganicanti-reflective coating formed thereon by a CVD process or the like, andfurthermore, on the coated substrate, an underlayer film may be formedfrom the resist underlayer film-forming composition of the presentinvention.

Sometimes, depending on the wavelength of light used in a lithographyprocess, the resist underlayer film formed from the resist underlayerfilm-forming composition of the present invention absorbs the light. Inthis case, the resist underlayer film can function as an anti-reflectivecoating having the effect of preventing light reflected from asubstrate. Furthermore, the resist underlayer film formed from theresist underlayer film-forming composition of the present invention canbe used as, for example, a layer for preventing the interaction betweena substrate and a photoresist; a layer having the function of preventinga material used for a photoresist or a substance produced at the time ofexposing a photoresist to light from having an adverse effect on asubstrate; a layer having the function of preventing a substanceproduced from a substrate at the time of heating and baking fromdiffusing to a photoresist serving as an upper layer; a barrier layerfor reducing the effect of poisoning a photoresist layer by asemiconductor substrate dielectric layer; or the like.

In the case where a resist underlayer film formed from the resistunderlayer film-forming composition functions as a hard mask, achromophore suitable for absorption of KrF laser is selected forlithography using the exposure wavelength of KrF (248 nm;). A condensedring structures of, for example, anthracene and phenanthrene and anaphthalimide structure are well known as such chromophores for KrFlaser, and these conventional chromophores lead to a larger molecularweight, and therefore cause difficulties in purification bydistillation, and hence, the control of metals as impurities in themanufacture of semiconductors was difficult.

The composition of the present invention includes a hydrolyzable silanehaving a structure in which O (oxygen atom) or S (sulfur atom) isattached to a benzene ring as a chromophore, and this silane absorbs KrFlaser, and furthermore, has a low molecular weight, and accordingly canbe easily purified by distillation. Therefore, the use of suchchromophores allows a hydrolysis-condensation product of a hydrolyzablesilane having a low impurity metal content to be used for theabove-mentioned resist underlayer film-forming composition, whereby asemiconductor product containing less impurities can be manufactured.

Furthermore, the resist underlayer film formed from the resistunderlayer film-forming composition of the present invention can beapplied to a substrate having via holes formed therein for use in thedual-damascene process, and can be used as an embedding material to fillup the holes. Furthermore, the resist underlayer film can be used as aflattening material to make the surface of a semiconductor substratehaving projections and depressions flat.

Furthermore, the resist underlayer film serving as an underlayer filmfor EUV resist can be used for the purposes mentioned below, besides asa hard mask. That is, the above-mentioned resist underlayer film-formingcomposition can be used for an anti-reflective underlayer coating forEUV resist that can prevent exposure light undesirable for EUV exposure(wavelength of 13.5 nm), such as UV and DUV mentioned above (ArF laser,KrF laser), from reflecting from a substrate or an interface, withoutintermixing with the EUV resist. The resist underlayer film canefficiently prevent the reflection at the underlayer of EUV resist. Whenused as an underlayer film for EUV resist, the resist underlayer filmcan be processed in the same manner as for an underlayer film forphotoresists.

Furthermore, the present invention relates to a silane of Formula (1′).R¹ _(a)R² _(b)Si(R³)_(4−(a+b))  Formula (1′)

In Formula (1′), R¹ is an organic group of Formula (2′):

and bonded to a silicon atom through a Si—C bond. R² is an alkyl group,an aryl group, a halogenated alkyl group, a halogenated aryl group, analkoxyaryl group, an alkenyl group, or an organic group having an epoxygroup, an acryloyl group, a methacryloyl group, a mercapto group, anamino group, or a cyano group, and is bonded to a silicon atom through aSi—C bond. R³ is an alkoxy group, an acyloxy group, or a halogen group.a is an integer of 1, b is an integer of 0 to 2, and a b is an integerof 1 to 3.

In Formula (2′), each of X and Y is an oxygen atom or a sulfur atom.However, X and Y are not the same atom at the same time. That is, in thepresent invention, X is an oxygen atom and Y is a sulfur atom, or,alternatively, X is a sulfur atom and Y is an oxygen atom.

R⁶ is an optionally substituted C₁₋₁₀ alkyl group, R⁴ is an optionallysubstituted C₁₋₁₀ alkylene group, and R⁵ is an optionally substitutedC₁₋₁₀ alkyl group. n is an integer of 0 to 4.

Examples of the alkyl group, the aryl group, the halogenated alkylgroup, the halogenated aryl group, the alkoxyaryl group, the alkenylgroup, or the organic group having an epoxy group, an acryloyl group, amethacryloyl group, a mercapto group, an amino group, or a cyano group,the alkoxy group, the acyloxy group, and the halogen group, which aredefined in Formula (1′) and Formula (2′) above, include theabove-mentioned examples.

EXAMPLES

(Synthesis of Compound 1)

Into a 300-ml three-neck flask equipped with a magnetic stirrer, 25.0 gof 4-(methylthio)phenol, 7.13 g of sodium hydroxide, 50 g of toluene,and 50 g of N-methylpyrrolidone (hereinafter, also referred to as NMP)were introduced, and allowed to react in an oil bath at 130° C. for 4hours while water and the toluene were removed. To the solution, 37.94 gof chloromethyltriethoxysilane was added dropwise, and heated andstirred at 130° C. for 4 hours. The obtained solution was cooled to roomtemperature and transferred to a separating funnel, and 120 g of tolueneand 90 g of water were added thereto to wash an organic phase. After thewashing was repeated 3 times, magnesium sulfate was added to the organicphase and dried, followed by filtration, and the solvent was removed byevaporation to obtain a crude product. The crude product was thenpurified by distillation under reduced pressure to obtain 30 g ofCompound 1 as a target product.

¹H-NMR (500 MHz, DMSO-d₆): 1.19 ppm (t, 9H), 2.42 ppm (s, 3H), 3.68 ppm(s, 2H), 3.86 ppm (q, 6H), 6.95 (d, 2H), 7.24 ppm (d, 2H)

(Synthesis of Compound 2)

Into a 300-ml three-neck flask equipped with a magnetic stirrer, 25.0 gof 4-(trifluoromethylthio)phenol, 5.15 g of sodium hydroxide, 50 g oftoluene, and 50 g of NMP were introduced, and allowed to react in an oilbath at 130° C. for 4 hours while water and the toluene were removed. Tothe solution, 27.39 g of chloromethyltriethoxysilane was added dropwise,and heated and stirred at 130° C. for 4 hours. The obtained solution wascooled to room temperature and transferred to a separating funnel, and120 g of toluene and 90 g of water were added thereto to wash an organicphase. After the washing was repeated 3 times, magnesium sulfate wasadded to the organic phase and dried, followed by filtration, and thesolvent was removed by evaporation to obtain a crude product. The crudeproduct was then purified by distillation under reduced pressure toobtain 2.5 g of Compound 2 as a target product.

¹H-NMR (500 MHz, DMSO-d₆): 1.19 ppm (t, 914), 3.78 ppm (s, 2H), 3.87 ppm(q, 6H), 7.13 (d, 2H), 7.60 ppm (d, 2H)

(Synthesis of Compound 3)

Into a 300-ml three-neck flask equipped with a magnetic stirrer, 25.0 g3-methyl-4-(methylthio)phenol, 6.48 g of sodium hydroxide, 50 g oftoluene, and 50 g of NMP were introduced, and allowed to react in an oilbath at 130° C. for 4 hours while water and the toluene were removed. Tothe solution, 34.49 g of chloromethyltriethoxysilane was added dropwise,and heated and stirred at 130° C. for 4 hours. The obtained solution wascooled to room temperature and transferred to a separating funnel, and120 g of toluene and 90 g of water were added thereto to wash an organicphase. After the washing was repeated 3 times, magnesium sulfate wasadded to the organic phase and dried, followed by filtration, and thesolvent was removed by evaporation to obtain a crude product. The crudeproduct was then purified by distillation under reduced pressure toobtain 35 g of Compound 3 as a target product.

¹H-NMR (500 MHz, DMSO-d₆): 1.20 ppm (t, 9H), 2.29 ppm (s, 3H), 2.37 ppm(s, 3H), 3.67 ppm (s, 2H), 3.86 ppm (q, 6H), 6.84 (d, 1H), 6.89 (d,114), 7.18 ppm (d, 1H)

(Synthesis of Compound 4)

Into a 300-ml three-neck flask equipped with a magnetic stirrer, 25.0 gof 3-methoxybenzenethiol, 7.13 g of sodium hydroxide, 50 g of toluene,and 50 g of NMP were introduced, and allowed to react in an oil bath at130° C. for 4 hours while water and the toluene were removed. To thesolution, 37.94 g of chloromethyltriethoxysilane was added dropwise, andheated and stirred at 130° C. for 4 hours. The obtained solution wascooled to room temperature and transferred to a separating funnel, and120 g of toluene and 90 g of water were added thereto to wash an organicphase. After the washing was repeated 3 times, magnesium sulfate wasadded to the organic phase and dried, followed by filtration, and thesolvent was removed by evaporation to obtain a crude product. The crudeproduct was then purified by distillation under reduced pressure toobtain 16 g of Compound 4 as a target product.

¹H-NMR (500 MHz, DMSO-d₆): 1.19 ppm (t, 9H), 2.33 ppm (s, 2H), 3.75 ppm(s, 3H), 3.83 ppm (q, 6H), 6.70 (d, 1H), 6.86 (d, 2H), 7.20 ppm (t, 1H)

(Synthesis of Compound 5)

Into a 300-ml three-neck flask equipped with a magnetic stirrer, 25.0 gof 4-methoxybenzenethiol, 7.13 g of sodium hydroxide, 50 g of toluene,and 50 g of NMP were introduced, and allowed to react in an oil bath at130° C. for 4 hours while water and the toluene were removed. To thesolution, 37.94 g of chloromethyltriethoxysilane was added dropwise, andheated and stirred at 130° C. for 4 hours. The obtained solution wascooled to room temperature and transferred to a separating funnel, and120 g of toluene and 90 g of water were added thereto to wash an organicphase. After the washing was repeated 3 times, magnesium sulfate wasadded to the organic phase and dried, followed by filtration, and thesolvent was removed by evaporation to obtain a crude product. The crudeproduct was then purified by distillation under reduced pressure toobtain 20 g of Compound 5 as a target product.

¹H-NMR (500 MHz, DMSO-d₆): 1.18 ppm (t, 9H), 2.29 ppm (s, 2H), 3.73 ppm(s, 3H), 3.82 ppm (q, 6H), 6.90 (d, 2H), 7.28 ppm (d, 2H)

(Synthesis of Compound 6)

Into a 300-ml three-neck flask equipped with a magnetic stirrer, 25.0 gof 2-(methylthio)phenol, 7.13 g of sodium hydroxide, 50 g of toluene,and 50 g of NMP were introduced, and allowed to react in an oil bath at130° C. for 4 hours while water and the toluene were removed. To thesolution, 37.94 g of chloromethyltriethoxysilane was added dropwise, andheated and stirred at 130° C. for 4 hours. The obtained solution wascooled to room temperature and transferred to a separating funnel, and120 g of toluene and 90 g of water were added thereto to wash an organicphase. After the washing was repeated 3 times, magnesium sulfate wasadded to the organic phase and dried, followed by filtration, and thesolvent was removed by evaporation to obtain a crude product. The crudeproduct was then purified by distillation under reduced pressure toobtain 20 g of Compound 6 as a target product.

¹H-NMR (500 MHz, DMSO-d₆): 1.18 ppm (t, 9H), 2.37 ppm (s, 3H), 3.73 ppm(s, 2H), 3.88 ppm (q, 6H), 6.95 (t, 1H), 7.02-7.18 ppm (m, 3H)

(Synthesis of Comparative Compound 1)

Into a 300-ml three-neck flask equipped with a magnetic stirrer, 25.0 gof 4-methoxy phenol, 8.05 g of sodium hydroxide, 50 g of toluene, and 50g of NMP were introduced, and allowed to react in an oil bath at 130 for4 hours while water and the toluene were removed. To the solution, 42.84g of chloromethyltriethoxysilane was added dropwise, and heated andstirred at 130° C. for 4 hours. The obtained solution was cooled to roomtemperature and transferred to a separating funnel, and 120 g of tolueneand 90 g of water were added thereto to wash an organic phase. After thewashing was repeated 3 times, magnesium sulfate was added to the organicphase and dried, followed by filtration, and the solvent was removed byevaporation to obtain a crude product. The crude product was thenpurified by distillation under reduced pressure to obtain, g ofComparative Compound 1 as a target product.

¹H-NMR (500 MHz, DMSO-d₆): 1.19 ppm (t, 9H), 3.63 ppm (s, 2H), 3.70 ppm(s, 3H), 3.86 ppm (q, 6H), 6.85 (d, 2H), 6.91 ppm (d, 2H)

Synthesis Example 1

5.24 g (10% by mole of the whole of the silane) of Compound 1, 25.86 g(75% by mole of the whole of the silane) of tetraethoxysilane, 4.43 g(15% by mole of the whole of the silane) of methyltriethoxysilane, and53.29 g of acetone were introduced into a 300-ml flask, and, while themixed solution was stirred with a magnetic stirrer, 11.19 g of 0.01mol/l hydrochloric acid was added dropwise to the mixed solution. Afterthe addition, the flask is transferred to an oil bath adjusted to 85°C., and under warming-reflux, the solution was allowed to react for 240minutes. The reaction solution was then cooled to room temperature. Tothe reaction solution, 72.00 g of propylene glycol monomethyl etheracetate was added, and then, ethanol as a reaction by-product, water,hydrochloric acid, and acetone were removed therefrom by distillationunder reduced pressure, and the resultant solution was concentrated toobtain a hydrolysis-condensation product (polymer) propylene glycolmonomethyl ether acetate solution. The solution was adjusted so as tocontain solid residues in a proportion of 30% by weight at 140° C. Theobtained polymer corresponds to Formula (3-1), and the weight-averagemolecular weight measured by GPC in terms of polystyrene was Mw 1,500.This polymer is referred to as P1.

Synthesis Examples 2 to 10 and Comparative Synthesis Examples 1 to 2were carried out in the same manner as in Synthesis Example 1. Table 1shows each component and the usage amount thereof.

A polymer obtained in Synthesis Example 2 corresponds to Formula (3-2),and had a weight-average molecular weight of 1,800. This polymer isreferred to as P2. A polymer obtained in Synthesis Example 3 correspondsto Formula (3-3), and had a weight-average molecular weight of 1,800.This polymer is referred to as P3. A polymer obtained in SynthesisExample 4 corresponds to Formula (3-4), and had a weight-averagemolecular weight of 1,600. This polymer is referred to as P4. A polymerobtained in Synthesis Example 5 corresponds to Formula (3-5), and had aweight-average molecular weight of 1,700. This polymer is referred to asP5. A polymer obtained in Synthesis Example 6 corresponds to Formula(3-6), and had a weight-average molecular weight of 1,700. This polymeris referred to as P6. A polymer obtained in Synthesis Example 7corresponds to Formula (3-7), and had a weight-average molecular weightof 1,700. This polymer is referred to as P7. A polymer obtained inSynthesis Example 8 corresponds to Formula (3-8), and had aweight-average molecular weight of 1,700. This polymer is referred to asP8. A polymer obtained in Synthesis Example 9 corresponds to Formula(3-9), and had a weight-average molecular weight of 2,000. This polymeris referred to as P9. A polymer obtained in Synthesis Example 10corresponds to Formula (3-9), and had a weight-average molecular weightof 1,600. This polymer is referred to as P10.

A polymer obtained in Comparative Synthesis Example 1 corresponds toFormula (4-1), and had a weight-average molecular weight of 1,700. Thispolymer is referred to as RP1.

A polymer obtained in Comparative Synthesis Example 2 corresponds toFormula (3-6), and had a weight-average molecular weight of 1,600. Thispolymer is referred to as RP2.

In Table 1, TEOS is tetraethoxysilane, MTEOS is methyltriethoxysilane,MeOPSP is 3-(4-methoxyphenylsulfonyl)propyltriethoxysilane, and MeOBSAis 4-methoxy-N-(3-(triethoxysilyl)propyl)benzenesulfonamide. Aciddenotes an HCl aqueous solution having a concentration of 0.01 M.

[Table 1]

TABLE 1 Synthesis Example 1 Compound 1 TEOS MTEOS Acid Solvent (acetone)5.24 g 25.86 g 4.43 g 11.19 g 53.29 g Synthesis Example 2 Compound 2TEOS MTEOS Acid Solvent (acetone) 6.00 g 25.30 g 4.33 g 10.94 g 53.44 gSynthesis Example 3 Compound 3 TEOS MTEOS Acid Solvent (acetone) 5.24 g25.86 g 4.43 g 11.19 g 53.29 g Synthesis Example 4 Compound 4 TEOS MTEOSAcid Solvent (acetone) 5.44 g 25.71 g 4.40 g 11.12 g 53.33 g SynthesisExample 5 Compound 5 TEOS MTEOS Acid Solvent (acetone) 5.24 g 25.86 g4.43 g 11.19 g 53.33 g Synthesis Example 6 Compound 6 TEOS MTEOS AcidSolvent (acetone) 5.24 g 25.86 g 4.43 g 11.19 g 53.33 g SynthesisExample 7 Compound 1 TEOS MTEOS Acid Solvent (acetone) 5.20 g 25.65 g4.10 g 11.10 g 53.34 g MeOPSP 0.62 g Synthesis Example 8 Compound 1 TEOSMTEOS Acid Solvent (acetone) 5.22 g 25.75 g 4.26 g 11.14 g 53.32 gMeOBSA 0.32 g Synthesis Example 9 Compound 1 TEOS MTEOS Acid Solvent(acetone) 14.20 g  21.81 g —  9.97 g 54.02 g Synthesis Example 10Compound 1 TEOS MTEOS Acid Solvent (acetone) 22.00 g  14.49 g —  8.77 g54.74 g Comparative Synthesis Example 1 Comparative Compound 1 TEOSMTEOS Acid Solvent (acetone) 5.00 g 26.03 g 4.46 g 11.26 g 53.24 gComparative Synthesis Example 2 Compound 6 TEOS MTEOS Acid Solvent(acetone) 2.43 g 26.70 g 6.25 g 11.55 g 53.07 g

(Preparation of resist underlayer film-forming composition)

Each of the silicon-containing polymers obtained in Synthesis Examples 1to 10 and Comparative Synthesis Examples 1 and 2 above was mixed with anacid, a curing catalyst, an additive, a solvent, and water so as toachieve the corresponding one of ratios shown in Table 2, and each ofthe mixtures was filtered with a 0.02-μm fluororesin filter to prepare asolution of a resist underlayer film-forming composition. The ratios ofthe polymers in Table 2 each refer not to the masses of the respectivepolymer solutions, but to the mass of the polymers themselves.

In Table 2, MA is maleic acid, Curing Catalyst C1 isN-(3-triethoxysilylpropyl)-4,5-dihydroimidazole (abbreviated asIMIDTEOS), Curing Catalyst C2 is benzyltriethylammonium chloride(abbreviated as BTEAC), Curing Catalyst C3 is triphenylsulfonium maleate(abbreviated as TPSMA), Curing Catalyst C4 is triphenylsulfonium nitrate(abbreviated as TPSNO3), Additive A1 is triphenylsulfoniumtrifluoromethanesulfonate (abbreviated as TPS105), Additive A2 is R-40LM(manufactured by DIC Corporation, having a fluorine-based surfactant asan ingredient), Solvent S1 is propylene glycol monomethyl ether(abbreviated as PGME), Solvent S2 is propylene glycol monoethyl ether(abbreviated as PGEE), and Solvent S3 is propylene glycol monomethylether acetate (abbreviated as PGMEA). Ultrapure water is used as water.Each of the addition amounts is expressed using part by mass.

[Table 2]

TABLE 2 Curing Polymer Acid catalyst Additive Solvent Water Example 1 P1MA C1 S1 S2 S3 water (part by mass) 4 0.04 0.024 5 73 10 12 Example 2 P2MA C1 S1 S2 S3 water (part by mass) 4 0.04 0.024 5 73 10 12 Example 3 P3MA C1 S1 S2 S3 water (part by mass) 4 0.04 0.024 5 73 10 12 Example 4 P4MA C1 S1 S2 S3 water (part by mass) 4 0.04 0.024 5 73 10 12 Example 5 P5MA C1 S1 S2 S3 water (part by mass) 4 0.04 0.024 5 73 10 12 Example 6 P6MA C1 S1 S2 S3 water (part by mass) 4 0.04 0.024 5 73 10 12 Example 7 P1MA C2 S1 S2 S3 water (part by mass) 4 0.04 0.024 5 73 10 12 Example 8 P1MA C2 A1 S1 S2 S3 water (part by mass) 4 0.04 0.024 0.04 5 73 10 12Example 9 P1 MA C3 A2 S1 S2 S3 water (part by mass) 4 0.04 0.04 0.04 573 10 12 Example 10 P1 MA C4 A2 S1 S2 S3 water (part by mass) 4 0.040.04 0.04 5 73 10 12 Example 11 P7 MA C1 A2 S1 S2 S3 water (part bymass) 4 0.04 0.024 0.04 5 73 10 12 Example 12 P8 MA C1 A2 S1 S2 S3 water(part by mass) 4 0.04 0.024 0.04 5 73 10 12 Example 13 P9 MA C2 S1 S2 S3water (part by mass) 4 0.04 0.024 5 73 10 12 Example 14 P10 MA C2 S1 S2S3 water (part by mass) 4 0.04 0.024 5 73 10 12 Comparative Example 1RP1 MA C1 S1 S2 S3 water (part by mass) 4 0.04 0.024 5 73 10 12Comparative Example 2 RP2 MA C1 S1 S2 S3 water (part by mass) 4 0.040.024 5 73 10 12

(Preparation of Organic Underlayer Film (Layer A) Forming Composition)

Under an atmosphere of nitrogen, carbazole (6.69 g, 0.040 mol,manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), andp-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured byTokyo Chemical Industry Co., Ltd.) were introduced into a 100-mlfour-neck flask, and 1,4-dioxane (6.69 g, manufactured by KANTO CHEMICALCO., INC.) was charged therein and stirred. The resultant mixture wasdissolved with the temperature increased to 100° C. to initiatepolymerization. After 24 hours, the product was left cool to 60° C., andthen, chloroform (34 g, manufactured by KANTO CHEMICAL CO., INC.) wasadded to dilute the product, and the resultant product wasreprecipitated in methanol (168 g, manufactured by KANTO CHEMICAL CO.,INC.). The obtained precipitate was filtered and dried with a vacuumdrier at 80° C. for 24 hours, yielding in 9.37 g of a polymer (Formula(E-1), hereinafter abbreviated as PCzFL) as a target product.

The measurement results of ¹H-NMR of PCzFL were as follows.

¹H-NMR (400 MHz, DMSO-d₆): 57.03-7.55 (br, 12H), δ 7.61-8.10 (br, 4H), δ11.18 (br, 1H)

The weight average molecular weight Mw of PCzFL measured by GPC in termsof polystyrene was 2,800, and the degree of poly-distribution Mw/Mn was1.77.

20 g of the obtained resin was mixed with 3.0 g of tetramethoxymethylglycoluril (the trade name Powderlink 1174, manufactured by Mitsui CytecLtd.) as a crosslinking agent, 0.30 g of pyridinium p-toluenesulfonateas a catalyst, and 0.06 g of MEGAFAC R-40LM (the trade name,manufactured by DIC Corporation) as a surfactant. The mixture wasdissolved in 88 g of propylene glycol monomethyl ether acetate to form asolution. The solution was then filtered with a polyethylene microfilterhaving a pore size of 0.10 μm, and further filtered with a polyethylenemicrofilter having a pore size of 0.05 μm to prepare a solution of anorganic underlayer film (Layer A) forming composition used for alithography process using a multilayer film.

(Optical Constant Measurement)

Each of the Si-containing resist underlayer film-forming compositionsprepared in Examples 1 to 14 and Comparative Examples 1 and 2 wasapplied onto a silicon wafer by a spinner. The coated silicon waferseach were heated on a hot plate at 215° C. for 1 minute to form therespective Si-containing resist underlayer films (with a film thicknessof 0.05 μm). Then, the refractive indexes (n value) and the opticalabsorption coefficients (also referred to as k value or attenuationcoefficient) at wavelengths of 193 nm and 248 nm of these resistunderlayer films were measured using a spectroscopic ellipsometer(VUV-VASEVU-302, manufactured by J. A. Woollam Co.). Table 3 shows theresults.

[Table 3]

TABLE 3 Refractive index n and optical absorption coefficient k atwavelengths of 193 nm and 248 nm n/k (measured n/k (measured at 193 nm)at 248 nm) Example 1 1.55/0.19 1.55/0.07 Example 2 1.50/0.18 1.57/0.07Example 3 1.51/0.15 1.57/0.07 Example 4 1.56/0.11 1.56/0.05 Example 51.55/0.18 1.55/0.06 Example 6 1.55/0.18 1.55/0.05 Example 7 1.55/0.191.55/0.07 Example 8 1.55/0.20 1.55/0.08 Example 9 1.55/0.20 1.55/0.08Example 10 1.55/0.20 1.55/0.08 Example 11 1.57/0.21 1.56/0.08 Example 121.55/0.19 1.55/0.07 Example 13 1.61/0.40 1.64/0.14 Example 14 1.64/0.491.68/0.17 Comparative Example 1 1.58/0.23 1.55/0.00 Comparative Example2 1.54/0.10 1.55/0.02

(Measurement of Dry Etching Rate)

For the measurement of dry etching rate, the following etcher andetching gas were used.

ES401 (manufactured by NIPPON SCIENTIFIC Co. Ltd.): CF₄

RIE-10NR (manufactured by SAMCO INC.): O₂

The solutions of the Si-containing resist underlayer film-formingcompositions prepared in Examples 1 to 14 and Comparative Examples 1 and2 were each applied onto a silicon wafer by a spinner. The coatedsilicon wafer was heated on a hot plate at 215° C. for 1 minute to forma Si-containing resist underlayer film (Layer B). Furthermore, likewise,the organic underlayer film (Layer A) forming composition was applied tothe silicon wafer by a spinner to form an organic underlayer film (LayerA) (with a film thickness of 0.20 μm) on the wafer. Using O₂ gas as anetching gas, the dry etching rates were measured, and comparisonsbetween the dry etching rate of the organic underlayer film (Layer A)and the respective dry etching rates of the Si-containing resistunderlayer films of Examples 1 to 14 and Comparative Examples 1 and 2were performed. The resistance to the oxygen-based gas (O₂ gas) wasexpressed by the etching rate ratio of [Si-containing resist underlayerfilm (Layer B)]/[organic underlayer film (Layer A)] (Table 4).

Furthermore, the solutions of the Si-containing resist underlayerfilm-forming composition prepared in Examples 1 to 14 and ComparativeExamples 1 and 2 were each applied onto a silicon water by a spinner.The coated silicon wafer was heated on a hot plate at 215° C. for 1minute to form a Si-containing resist underlayer film (Layer B).Furthermore, likewise, the organic underlayer film (Layer A) formingcomposition was applied to the silicon wafer by a spinner to form anorganic underlayer film (Layer A) (with a film thickness of 0.20 μm) onthe wafer. Then, using a fluorine-based gas (CF₄ gas), the dry etchingrates (etching rate: nm/min) were measured. In the same manner as theabove, the resistance to the fluorine-based gas (CF₄ gas) was expressedby the etching rate ratio of [Si-containing resist underlayer film(Layer B)]/[organic underlayer film (Layer A)] (Table 4).

[Evaluation of Pattern Shape]

The organic underlayer film (Layer A) forming composition was appliedonto a silicon wafer, followed by baking on a hot plate at 240° C. for60 seconds to obtain an organic underlayer film (Layer A) with a filmthickness of 200 nm. On the organic underlayer film, each of theSi-containing resist underlayer film-forming compositions prepared byExamples 1 to 14 and Comparative Examples 1 and 2 was applied by aspinner. The coated silicon wafer was then baked on a hot plate at 215°C. for 1 minute to form a resist underlayer film (with a film thicknessof 0.06 μm). Onto this resist underlayer film, a commercially availablephotoresist solution (trade name: TDUR-P3435LP, manufactured by TOKYOOHKA KOGYO CO., LTD.) was applied by a spinner, and heated on a hotplate at 90° C. for 1 minute to form a photoresist film (with a filmthickness of 0.25 μm). Next, using NSR-S205C, a lens scanning steppermanufactured by NIKON CORPORATION, (with a wavelength of 248 nm, NA:0.75, σ: 0.85 (CONVENTIONAL)), the photoresist film was exposed to lightthrough a mask set so that the line width of a photoresist pattern andthe intervals between lines of the pattern were 0.16 μm afterdevelopment. Subsequently, “post-exposure heating” was carried out on ahot plate at 110° C. for 1 minute. After cooled, the photoresist filmwas developed using a 2.38% tetramethylammonium hydroxide solution as adeveloping solution. The shape of the resist after the development wasevaluated (Table 4).

[Table 4]

TABLE 4 CF₄ O₂ Resist shape Example 1 24.0 0.03 straight Example 2 25.00.04 straight Example 3 24.0 0.03 straight Example 4 24.0 0.03 straightExample 5 24.0 0.03 straight Example 6 24.0 0.03 straight Example 7 24.00.03 straight Example 8 24.0 0.03 straight Example 9 24.0 0.03 straightExample 10 24.0 0.03 straight Example 11 23.5 0.03 straight Example 1224.0 0.03 straight Example 13 25.5 0.04 straight Example 14 26.0 0.06straight Comparative Example 1 23.5 0.03 multiple light exposure shapedue to standing wave Comparative Example 2 24.0 0.02 multiple lightexposure shape due to standing wave

INDUSTRIAL APPLICABILITY

The resist underlayer film-forming composition of the present inventionincludes a hydrolyzable silane having a structure in which O (oxygenatom or S (sulfur atom) is attached to a benzene ring as a chromophore.This silane can absorb KrF laser and, furthermore, has a low molecularweight, thereby being capable of easy purification by distillation.Therefore, a semiconductor product containing less impurities can bemanufactured from the above-mentioned resist underlayer film-formingcomposition including a hydrolysis-condensation product of ahydrolyzable silane including such chromophores and having a lowimpurity metal content.

The invention claimed is:
 1. A resist underlayer film-formingcomposition for lithography, the composition comprising, as a silane, ahydrolyzable silane, a hydrolysis product thereof, or ahydrolysis-condensation product thereof, wherein the hydrolyzable silaneis a combination of a hydrolyzable silane of Formula (1) and anotherhydrolyzable silane:R¹ _(a)R² _(b)Si(R³)_(4−(a+b))  Formula (1) wherein R¹ is an organicgroup of Formula (2):

wherein each of X and Y is an oxygen atom or a sulfur atom, providedthat X and Y are not the same atom at the same time; R⁶ is an optionallysubstituted C₁₋₁₀ alkyl group; R⁴ is an optionally substituted C₁₋₁₀alkylene group; R⁵ is an optionally substituted C₁₋₁₀ alkyl group; and nis an integer of 0 to 4, and R¹ is bonded to the silicon atom of Formula(1) through a Si—C bond; R² is an alkyl group, an aryl group, ahalogenated alkyl group, a halogenated aryl group, an alkoxyaryl group,an alkenyl group, or an organic group having an epoxy group, an acryloylgroup, a methacryloyl group, a mercapto group, an amino group, or acyano group, and is bonded to the silicon atom through a Si—C bond; R³is an alkoxy group, an acyloxy group, or a halogen group; a is aninteger of 1; b is an integer of 0 to 2; a+b is an integer of 1 to 3,the other hydrolyzable silane is at least one hydrolyzable silaneselected from the group consisting of a hydrolyzable silane of Formula(3):R⁷ _(c)Si(R⁸)_(4−c)  Formula (3) wherein R⁷ is an alkyl group, an arylgroup, a halogenated alkyl group, a halogenated aryl group, analkoxyaryl group, an alkenyl group, or an organic group having an epoxygroup, an acryloyl group, a methacryloyl group, a mercapto group, or acyano group, and is bonded to the silicon atom of Formula (3) through aSi—C bond; R⁸ is an alkoxy group, an acyloxy group, or a halogen group;and c is an integer of 0 to 3, and a hydrolyzable silane of Formula (4):[R⁹ _(d)Si(R¹⁰)_(3−d)]₂Y^(R) _(e)  Formula (4) wherein R⁹ is an alkylgroup and is bonded to the silicon atom of Formula (4) through a Si—Cbond; R¹⁰ is an alkoxy group, an acyloxy group, or a halogen group;Y^(R) is an alkylene group or an arylene group; d is an integer of 0 or1; and e is an integer of 0 or 1), and a ratio of sulfur atoms tosilicon atoms is 7% by mole or more in the whole of the silane.
 2. Theresist underlayer film-forming composition for lithography according toclaim 1, wherein the ratio of sulfur atoms to silicon atoms is 7% bymole to 50% by mole in the whole of the silane.
 3. The resist underlayerfilm-forming composition according to claim 1, the compositioncomprising, as an underlayer film-forming polymer, ahydrolysis-condensation product of a hydrolyzable silane comprising acombination of the hydrolyzable silane of Formula (1) and thehydrolyzable silane of Formula (3).
 4. The resist underlayerfilm-forming composition according to claim 1, further comprising anacid as a hydrolysis catalyst.
 5. The resist underlayer film-formingcomposition according to claim 1, further comprising water.
 6. A resistunderlayer film obtained by applying the resist underlayer film-formingcomposition as claimed in claim 1 onto a semiconductor substrate andbaking the applied resist underlayer film-forming composition.
 7. Amethod for manufacturing a semiconductor device, the method comprising:applying the resist underlayer film-forming composition as claimed inclaim 1 onto a semiconductor substrate, and baking the applied resistunderlayer film-forming composition to form a resist underlayer film;applying a resist composition onto the underlayer film to form a resistfilm; exposing the resist film to light; developing the resist after theexposure to obtain a resist pattern; etching the resist underlayer filmwith the resist pattern; and processing the semiconductor substrate withthe patterned resist underlayer film.
 8. A method for manufacturing asemiconductor device, the method comprising: forming an organicunderlayer film on a semiconductor substrate; applying the resistunderlayer film-forming composition as claimed in claim 1 onto theorganic underlayer film, and baking the applied resist underlayerfilm-forming composition to form a resist underlayer film; applying aresist composition onto the resist underlayer film to form a resistfilm; exposing the resist film to light; developing the resist after theexposure to obtain a resist pattern; etching the resist underlayer filmwith the resist pattern; etching the organic underlayer film with thepatterned resist underlayer film; and processing the semiconductorsubstrate with the patterned organic underlayer film.
 9. A resistunderlayer film-forming composition for lithography, the compositioncomprising, as a silane, a hydrolyzable silane, a hydrolysis productthereof, or a hydrolysis-condensation product thereof, wherein thehydrolyzable silane comprises a hydrolyzable silane of Formula (1):R¹ _(a)R² _(b)Si(R³)_(4−(a+b))  Formula (1) wherein R¹ is an organicgroup of Formula (2):

wherein each of X and Y is an oxygen atom or a sulfur atom, providedthat X and Y are not the same atom at the same time; R⁶ is an optionallysubstituted C₁₋₁₀ alkyl group; R⁴ is an optionally substituted C₁₋₁₀alkylene group; R⁵ is an optionally substituted C₁₋₁₀ alkyl group; and nis an integer of 0 to 4, and R¹ is bonded to the silicon atom of Formula(1) through a Si—C bond; R² is an alkyl group, an aryl group, ahalogenated alkyl group, a halogenated aryl group, an alkoxyaryl group,an alkenyl group, or an organic group having an epoxy group, an acryloylgroup, a methacryloyl group, a mercapto group, an amino group, or acyano group, and is bonded to the silicon atom through a Si—C bond; R³is an alkoxy group, an acyloxy group, or a halogen group; a is aninteger of 1; b is an integer of 0 to 2; and a+b is an integer of 1 to3, and a ratio of sulfur atoms to silicon atoms is 7% by mole or to 50%by mole in the whole of the silane.
 10. A resist underlayer film-formingcomposition for lithography, the composition comprising: water; and as asilane, a hydrolyzable silane, a hydrolysis product thereof, or ahydrolysis-condensation product thereof, wherein the hydrolyzable silanecomprises a hydrolyzable silane of Formula (1):R¹ _(a)R² _(b)Si(R³)_(4−(a+b))  Formula (1) wherein R¹ is an organicgroup of Formula (2):

wherein each of X and Y is an oxygen atom or a sulfur atom, providedthat X and Y are not the same atom at the same time; R⁶ is an optionallysubstituted C₁₋₁₀ alkyl group; R⁴ is an optionally substituted C₁₋₁₀alkylene group; R⁵ is an optionally substituted C₁₋₁₀ alkyl group; and nis an integer of 0 to 4, and R¹ is bonded to the silicon atom of Formula(1) through a Si—C bond; R² is an alkyl group, an aryl group, ahalogenated alkyl group, a halogenated aryl group, an alkoxyaryl group,an alkenyl group, or an organic group having an epoxy group, an acryloylgroup, a methacryloyl group, a mercapto group, an amino group, or acyano group, and is bonded to the silicon atom through a Si—C bond; R³is an alkoxy group, an acyloxy group, or a halogen group; a is aninteger of 1; b is an integer of 0 to 2; and a+b is an integer of 1 to3, and a ratio of sulfur atoms to silicon atoms is 7% by mole or more inthe whole of the silane.